Application of principal component analysis for the optimisation of lead(II) biosorption.

PubMed

Wajda, Łukasz; Duda-Chodak, Aleksandra; Tarko, Tomasz; Kamiński, Paweł

2017-10-03

Current study was focused on optimising lead(II) biosorption carried out by living cells of Arthrospira platensis using Principal Component Analysis. Various experimental conditions were considered: initial metal concentration (50 and 100 mg/l), solution pH (4.0, 4.5, 5.0, 5.5) and contact time (10, 20, 30, 40, 50 and 60 min) at constant rotary speed 200 rpm. It was found that when the biomass was separated from experimental solutions by the filtration, almost 50% of initial metal dose was removed by the filter paper. Moreover, pH was the most important parameter influencing examined processes. The Principal Component Analysis indicated that the most optimum conditions for lead(II) biosorption were metal initial concentration 100 mg/l, pH 4.5 and time 60 min. According to the analysis of the first component it might be stated that the lead(II) uptake increases in time. In overall, it was found to be useful for analysing data obtained in biosorption experiments and eliminating insignificant experimental conditions. Experimental data fitted Langmuir and Dubinin-Radushkevich models indicating that physical and chemical absorption take place at the same time. Further studies are necessary to verify how sorption-desorption cycles affect A. platensis cells.

Competitive Adsorption and Oxidation Behavior of Heavy Metals on nZVI Coated with TEOS.

PubMed

Eglal, Mahmoud M; Ramamurthy, Amruthur S

2015-11-01

Zero valent iron nanoparticle (nanofer ZVI) is a powerful substance due to its coating with tetraethyl orthosilicate (TEOS). Tetraethyl orthosilicate imparts higher reactivity and decreases particle agglomeration. The competitive removal and displacement of multi-metals are influenced by time, pH, and initial concentration, the presence and properties of competing metals ion in the solution. For both the isotherm and kinetic studies performed for multi-metal removal experiments, compared to Pb II and Cd II, Cu II experienced a higher removal rate during the initial 5 minutes. After 120 minutes, all metals achieved removal efficiency in the range of 95 to 99%. The results of single and competitive kinetic tests for all three metals during the initial 5 minutes indicated that the presence of other metals generally reduce removal efficiency of metals. Both kinetic test and electron dispersive spectroscope (EDS) studies found that Cu II gets removed faster than the other metals. Pseudo-second order behavior was noted for the multi-metal removal systems.

Influence of pH on Cr(VI) ions removal from aqueous solutions using carboxymethyl cellulose-based hydrogel as adsorbent

NASA Astrophysics Data System (ADS)

Anah, L.; Astrini, N.

2017-03-01

The major problem in heavy metal pollution is that these metals are not biodegradable and accordingly accumulate in the bodies of living organisms, causing dangerous diseases and serious cell disorder. According to World Health Organization (WHO), the long term exposure of Cr(VI) levels of over 0.1 ppm causes respiratory problems, liver and kidney damage, and carcinogenicity.Due to its easy operation and of various cheap adsorbents development, adsorption has been proved to be efficient and most economically attractive technique and feasible to the removal of toxic heavy metal from wastewater. The study aimed to report the removal of Cr(VI) ions from aqueous solutions through adsorption process using carboxymethyl cellulose-graft-poly(acrylic acid) (CMC-g-PAA) hydrogel as adsorbent.Effect of pH was studied to remove hexavalent chromium.Graft copolymerization of poly(acrylic acid) onto carboxymethyl cellulose was carried out in the presence of benzoyl peroxide redox initiator and methylenbisacrylamide as crosslinker agent. Batch experiments were carried out to investigate the effects ofinitial pH.The adsorption of Cr(VI) ions as a function of pH was conducted in the initial pH range of 1 to 8. The results indicated that acidic pH strongly favored the adsorption. The optimum pH for adsorption of Cr(VI) ranged from 1 to 3, and the maximum uptake of Cr(VI) from the solution was 6.53 mg/g at pH 1 and 30°C. FTIR spectroscopy, SEM analyses were performed on the adsorbent before and after Cr(VI) binding. All analyses confirmed the complexation of Cr(VI) ions on the adsorbent.

Biosorption of Hexavalent Chromium from Aqueous Medium with Opuntia Biomass

PubMed Central

2014-01-01

The biosorption of hexavalent chromium from aqueous solutions by Opuntia cladodes and ectodermis from cactus fruits was investigated. Both types of biomass are considered low-cost, natural, and ecofriendly biosorbents. Batch experiments were carried out to determine Cr(VI) biosorption capacity and the efficiency of the biosorption process under different pH, initial Cr(VI) concentration, and sorbent dosage. The biosorption of Cr(VI) by Opuntia biomass was highly pH dependent, favoring higher metal uptake at low pH. The higher biosorption capacity was exhibited at pH 2. The optimal conditions were obtained at a sorbent dosage of 1 g L−1 and initial metal concentration of 10 mg L−1. Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The rate constant, the initial biosorption rate, and the equilibrium biosorption capacity were determined. The experimental equilibrium data obtained were analyzed using two-parameter isotherm models (Langmuir, Freundlich, and Temkin). The Langmuir maximum monolayer biosorption capacity (q max) was 18.5 mg g−1 for cladodes and 16.4 mg g−1 for ectodermis. The results suggest that Opuntia biomass could be considered a promising low-cost biosorbent for the ecofriendly removal of Cr(VI) from aqueous systems. PMID:24982975

Treatment of mining waste leachate by the adsorption process using spent coffee grounds.

PubMed

Ayala, Julia; Fernández, Begoña

2018-02-15

The removal of heavy metals from mining waste leachate by spent coffee grounds has been investigated. In synthetic solutions, metal uptake was studied in batch adsorption experiments as a function of pH, contact time, initial metal concentration, adsorbent concentration, particle size, and the effect of co-ions (Na, K, Ca, Mg, Cu, Cd, Ni, Zn). Results showed that adsorption was significantly affected by pH, showing the highest affinity within a pH range of 5-7. Sorption of heavy metals reached equilibrium in 3 h. Removal percentages of metals ions increased with increasing dosage. Particle size did not have a significant influence on metal uptake. The adsorption of heavy metals was found to fit Langmuir and Freundlich isotherms. Maximum Zn, Cd and Ni uptake values were calculated as 10.22, 5.96 and 7.51 mg/g, respectively, using unwashed coffee grounds (UCG) as the adsorbent and 5.36, 4.28 and 4.37 mg/g when employing washed coffee grounds as the adsorbent. The presence of co-ions inhibited the uptake of heavy metals, divalent ions having a more negative effect than monovalent ions. The results obtained in the experiments with mining waste leachate showed that UCG is effective in removing heavy metals.

Mobilities and leachabilities of heavy metals in sludge with humus soil.

PubMed

Zhu, Rui; Wu, Min; Yang, Jian

2011-01-01

Chemical forms of Zn, Ni, Cu, and Pb in municipal sewage sludge were investigated by adding humus soil to sludge and by performing sequential extraction procedures. In the final sludge mixtures, Zn and Ni were mainly found in Fe/Mn oxide-bound (F3) and organic matter/sulfide-bound (F4) forms. For Zn, exchangeable (F1), carbonate-bound (F2), and F3 forms were transformed to F4 and residual forms (F5). For Ni, F1 and F2 forms were transformed to F1, F2, and F3 forms. Both Cu and Pb were strongly associated with the stable forms F4 and F5. For Cu, F2 and F3 forms were major contributors, while for Pb, F3 and F4 forms were major contributors to F5. Humus soil dosage and pH conditions in the sludge were strongly correlated with the forms of heavy metals. Five forms were used to evaluate metal mobilities in the initial and final sludge mixtures. The mobilities of the four heavy metals studied decreased after 28 days. The metal mobilities in the final sludge mixtures were ranked in the following order: Ni > Zn > Cu = Pb. Leaching tests showed that the mobilities of Zn and Ni in lower pH conditions (pH 4) were higher than those in higher pH conditions (pH 8).

Biosorption of Nickel from Industrial Wastewater using Zygnema sp.

NASA Astrophysics Data System (ADS)

Sivaprakash, Kanchana; Blessi T. L., Adlin; Madhavan, Jeyanthi

2015-12-01

Contamination of water sources with heavy metals is a very important pollution problem in the current scenario. Biosorption is an effective method for the removal of heavy metal ions from wastewaters. In this study, the removal of Nickel(II) ions from electroplating industrial wastewater using biosorbent prepared from fresh water algal biomass Zygnema was investigated under batch mode. The sorption efficiency of nickel on Zygnema sp. was evaluated as a function of time, pH and sorbent dosage. The Nickel(II) uptake was dependent on initial pH with pH 3 being the optimum value. For 100 mg/L initial Nickel(II) concentration, sorption equilibrium was attained at a contact time of 100 min. The sorbent dosage affected the biosorption efficiency and maximum removal of 76.4 % was obtained at a dosage of 7.5 g/L. From the performance studies, algal biosorbent Zygnema is found to be a valuable material for the removal of Nickel from industrial wastewater and a better substitute for the conventional adsorbents.

Assessing the suitability of the OECD 29 guidance document to investigate the transformation and dissolution of silver nanoparticles in aqueous media.

PubMed

Wasmuth, Claus; Rüdel, Heinz; Düring, Rolf-Alexander; Klawonn, Thorsten

2016-02-01

The OECD guidance document No. 29 was designed to determine the rate and extend to which metals can produce soluble available ionic metal species. This transformation/dissolution protocol was applied to silver nanomaterials. The results prove that concentrations of released Ag(+) at pH 8 were nearly similar at all three different loadings. At pH 6, the concentration of Ag(+) was almost the same at loadings of 10 and 100 mg L(-1) AgNPs. However, the study showed changes in concentrations of nanoparticles and aggregates (operationally defined as the fraction passing a 0.2 µm filter). At the higher pH both the concentrations in the test medium of Ag(+) and of AgNPs (fraction < 0.2 µm) decreased. After 7 days of test duration, 71 µg L(-1) of Ag(+) was found in pH 6 medium (initial loading of 100 mg L(-1)). In pH 8 medium a maximum concentration of 29 µg L(-1) Ag(+) was measured (initial loading of 10 mg L(-1)). The maximum transformation from AgNPs to Ag(+) was 2.7% (27 µg L(-1)) in pH 8 medium (loading of 1 mg L(-1)) after 7 days. At an initial loading of 100 mg L(-1) AgNPs in medium at pH 8, only 0.03% (30 µg L(-1)) were transformed to Ag(+) after 7 days. At the loading of 1 mg L(-1) AgNPs all silver concentrations remain relatively constant for the duration of the test after 7 until 28 days. The results reveal that only low concentrations of Ag(+) are released from AgNPs under the applied conditions. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Removal of some metal ions by activated carbon prepared from Phaseolus aureus hulls.

PubMed

Rao, M Madhava; Ramana, D K; Seshaiah, K; Wang, M C; Chien, S W Chang

2009-07-30

Removal of lead [Pb(II)], zinc [Zn(II)], copper [Cu(II)], and cadmium [Cd(II)] from aqueous solutions using activated carbon prepared from Phaseolus aureus hulls (ACPAH), an agricultural waste was studied. The influence of various parameters such as effect of pH, contact time, adsorbent dose, and initial concentration of metal ions on the removal was evaluated by batch method. The removal of metal ions by ACPAH was pH dependent and the optimum pH values were 7.0, 8.0, 7.0 and 6.0 for Cu(II), Cd(II), Zn(II), and Pb(II), respectively. The sorption isotherms were studied using Langmuir, Freundlich, Dubinin-Radushkevich (D-R), and Temkin isotherm models. The maximum adsorption capacity values of ACPAH for metal ions were 21.8 mg g(-1) for Pb(II), 21.2 mg g(-1) for Zn(II), 19.5 mg g(-1) for Cu(II), and 15.7 mg g(-1) for Cd(II). The experiments demonstrated that the removal of metal ions followed the pseudo-second-order kinetic model. Desorption experiments were carried out using HCl solution with a view to regenerate the spent adsorbent and to recover the adsorbed metal ions.

Evaluation of metal ion absorptive characteristics of three types of plastic sample bags used for pecipitation sampling

USGS Publications Warehouse

Good, A.B.; Schroder, L.J.

1984-01-01

Simulated precipitation samples containing 16 metal ions were prepared at 4 pH values. Absorptive characteristics of polypropylene, polyethylene, and polyester/polyolefin sacks were evaluated at pH 3.5, 4.0, 4.5, and 5.0. Simulated precipitation was in contact with the sacks for 17 days, and subsamples were removed for chemical analysis at 3, 7, 10, 14, and 17 days after initial contact. All three types of plastic sacks absorbed Fe throughout the entire pH range. Polypropylene and polyethylene absorbed Pb throughout the entire pH range; polyester/polyolefin sacks absorbed Pb at pH 4.0 or greater. All plastic sacks also absorbed Cu, Mo, and V at pH 4.5 and 5.0. Leaching the plastic sacks with 0.7 percent HNO3 did not result in 100 percent of Cu, Fe, Pb, and V. These sacks would be suitable collection vessels for Ba, Be, Ca, Cd, Co, Li, Mg, Mn, Na Sr and Zn in precipitation through the pH range of 3.5 to 5.0.

Effect of sulphur concentration on bioleaching of heavy metals from contaminated dredged sediments.

PubMed

Fang, D; Zhao, L; Yang, Z Q; Shan, H X; Gao, Y; Yang, Q

2009-11-01

The sulphur-based bioleaching process using sulphur-oxidizing bacteria (SOB) has been demonstrated to be a feasible technology for removing heavy metals from contaminated sediments, but the excess sulphur application will lead to the re-acidification of bioleached sediments. The objective of the present study was to examine the effect of sulphur concentration on the bioleaching of heavy metals from contaminated sediments, with the ultimate purpose of minimizing the sulphur addition. The results showed that the inoculation of 7% of indigenous SOB, containing 3.6 x 10(8) colony forming units (CFU) mL(-1), and addition of elemental sulphur as a substrate (0.5 to 7.0 g L(-1)) resulted in a sharp decrease in sediment pH from an initial pH 8.0 to pH 1.4-2.4 and an increase in ORP (oxidation-reduction potential) from -10 mV to 500 mV within 10 days of bioleaching. Although the increase in sulphur concentration enhanced the rates of pH reduction and ORP elevation, the bioleaching process with the addition of 3.0 g L(-1) of sulphur was already sufficient to reach conditions of acidity (pH < 2.0) and ORP (500 mV) necessary for a satisfactory removal of metals, and, at day 10, 71.8% of Cu, 58.2% of Zn, and 25.3% of Cr were removed from the sediments. During the bioleaching process, Zn removal increased with a reduction in pH, whereas the removal of Cu and Cr increased not only with a reduction in pH but also with an increase in ORP. Results of sequential selective extraction indicated that the final levels of metal removals were dependent on their speciation distribution in the original sediments, and after bioleaching those unremoved metals in the bioleached sediments mainly existed in the residual fraction.

The corrosion behavior of technetium metal exposed to aqueous sulfate and chloride solutions

DOE PAGES

Kolman, David Gary; Goff, George Scott; Cisneros, Michael Ruben; ...

2017-04-19

Here, metal waste forms are being studied as possible disposal forms for technetium and other fission products from spent nuclear fuel. As an initial step in assessing the viability of waste forms, technetium corrosion and passivity behavior was assessed across a broad pH spectrum (pH –1 to pH 13). Measurements indicate that the open circuit potential falls into the region of Tc +7 stability, more noble than the region of presumed passivity. Potentiodynamic polarization tests indicate that the Tc samples are not passive. Both electrochemical results and visual inspection suggest the presence of a nonprotective film. The corrosion rate ismore » relatively independent of pH and low, as measured by linear polarization resistance. No evidence of passivity was observed in the Tc +4 region of the potential-pH diagram following in-situ abrasion, suggesting that Tc does not passivate, regardless of potential.« less

The corrosion behavior of technetium metal exposed to aqueous sulfate and chloride solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kolman, David Gary; Goff, George Scott; Cisneros, Michael Ruben

Here, metal waste forms are being studied as possible disposal forms for technetium and other fission products from spent nuclear fuel. As an initial step in assessing the viability of waste forms, technetium corrosion and passivity behavior was assessed across a broad pH spectrum (pH –1 to pH 13). Measurements indicate that the open circuit potential falls into the region of Tc +7 stability, more noble than the region of presumed passivity. Potentiodynamic polarization tests indicate that the Tc samples are not passive. Both electrochemical results and visual inspection suggest the presence of a nonprotective film. The corrosion rate ismore » relatively independent of pH and low, as measured by linear polarization resistance. No evidence of passivity was observed in the Tc +4 region of the potential-pH diagram following in-situ abrasion, suggesting that Tc does not passivate, regardless of potential.« less

The use of macroalgae (Gracilaria changii) as bio-adsorbent for Copper (II) removal

NASA Astrophysics Data System (ADS)

Lavania-Baloo; Idayu, Nordin; Umar Salihi, Ibrahim; Zainoddin, Jamari

2017-05-01

Biosorption of heavy metals using marine macroalgae biomass can be an effective process and alternative to conventional methods. Activated carbon was developed from macroalgae (Gracilaria changii) and used as adsorbents for the removal of copper (II) from wastewater. Gracilaria changii based activated carbon (GCBAC) was prepared using muffle furnace at a constant temperature of 300 °C for 1 hour. Batch adsorption experiments were conducted to investigate the effets of important parameters such as pH, contact time, initial metal concentration and adsorbent dosage on the removal of Cu (II) from synthetic aqueous solution. Batch adsorption study shows that removal of Cu (II) using GCBAC relied upon pH, contact time, initial metal concentration and GCBAC dosage. The optimum conditions parameters were found to be pH 6.0, time of 60 minutes and GCBAC dosage of 0.3 g, respectively. Adsorption data was described better by Freundlich isotherm model with R2 value of 0.7936. The maximum Cu (II) adsorption capacity of GCBAC was found to be 0.07 mg/g. The experimental adsorption data obtained fitted well into Pseudo-second-order kinetic model, with R2 value near unity. Thus, GCBAC can be used as an effective adsorbent for the removal of Cu (II) from aqueous solution.

Utilization of rice husks modified by organomultiphosphonic acids as low-cost biosorbents for enhanced adsorption of heavy metal ions.

PubMed

Xu, Mingyu; Yin, Ping; Liu, Xiguang; Tang, Qinghua; Qu, Rongjun; Xu, Qiang

2013-12-01

Novel biosorbent materials (RH-2 and RH-3) obtained from agricultural waste materials rice husks (RH-1) were successfully developed through fast and facile esterification reactions with hydroxylethylidenediphosphonic acid and nitrilotrimethylenetriphosphonic acid, respectively. The present paper reported the feasibility of using RH-1, RH-2 and RH-3 for removal of heavy metals from simulated wastewater, the results revealed that the adsorption property of functionalized rice husks with organotriphosphonic acid RH-3 for Au(III) was very excellent, especially for gold ions. The combined effect of initial solution pH, RH-3 dosage and initial Au(III) concentration was investigated using response surface methodology (RSM), the results showed that initial Au(III) concentration exerted stronger influence on Au(III) uptake than initial pH and biomass dosage. The analysis of variance (ANOVA) of the quadratic model demonstrated that the model was highly significant, and under the optimum process conditions, the maximum adsorption capacity could reach 3.25 ± 0.07 mmol/g that is higher than other reported adsorbents. Copyright © 2013 Elsevier Ltd. All rights reserved.

Bioleaching of heavy metals from sewage sludge by indigenous iron-oxidizing microorganisms using ammonium ferrous sulfate and ferrous sulfate as energy sources: a comparative study.

PubMed

Pathak, Ashish; Dastidar, M G; Sreekrishnan, T R

2009-11-15

The potential of indigenous iron-oxidizing microorganisms enriched at initial neutral pH of the sewage sludge for bioleaching of heavy metals was investigated at initial neutral pH of the sludge using ammonium ferrous sulfate (FAS) and ferrous sulfate (FS) as an energy sources in two different sets of experiments. After 16 days of bioleaching, 56% Cu, 48% Ni, 68% Zn and 42% C were removed from the sludge using ammonium ferrous sulfate as an energy source. On the other hand, 64% Cu, 58% Ni, 76% Zn and 52% Cr were removed using ferrous sulfate. Further, 32% nitrogen and 24% phosphorus were leached from the sludge using ferrous sulfate, whereas only 22% nitrogen and 17% phosphorus were removed using ammonium ferrous sulfate. The BCR sequential extraction study on speciation of metals showed that using ammonium ferrous sulfate and ferrous sulfate, all the metals remained in bioleached sludge as stable form (F4 fraction). The results of the present study indicate that the bioleached sludge would be safer for land application. Also, the fertilizing property was largely conserved in the bioleached sludge using both the substrates.

Influence of sulfhydryl sites on metal binding by bacteria

NASA Astrophysics Data System (ADS)

Nell, Ryan M.; Fein, Jeremy B.

2017-02-01

The role of sulfhydryl sites within bacterial cell envelopes is still unknown, but the sites may control the fate and bioavailability of metals. Organic sulfhydryl compounds are important complexing ligands in aqueous systems and they can influence metal speciation in natural waters. Though representing only approximately 5-10% of the total available binding sites on bacterial surfaces, sulfhydryl sites exhibit high binding affinities for some metals. Due to the potential importance of bacterial sulfhydryl sites in natural systems, metal-bacterial sulfhydryl site binding constants must be determined in order to construct accurate models of the fate and distribution of metals in these systems. To date, only Cd-sulfhydryl binding has been quantified. In this study, the thermodynamic stabilities of Mn-, Co-, Ni-, Zn-, Sr- and Pb-sulfhydryl bacterial cell envelope complexes were determined for the bacterial species Shewanella oneidensis MR-1. Metal adsorption experiments were conducted as a function of both pH, ranging from 5.0 to 7.0, and metal loading, from 0.5 to 40.0 μmol/g (wet weight) bacteria, in batch experiments in order to determine if metal-sulfhydryl binding occurs. Initially, the data were used to calculate the value of the stability constants for the important metal-sulfhydryl bacterial complexes for each metal-loading condition studied, assuming a single binding reaction for the dominant metal-binding site type under the pH conditions of the experiments. For most of the metals that we studied, these calculated stability constant values increased significantly with decreasing metal loading, strongly suggesting that our initial assumption was not valid and that more than one type of binding occurs at the assumed binding site. We then modeled each dataset with two distinct site types with identical acidity constants: one site with a high metal-site stability constant value, which we take to represent metal-sulfhydryl binding and which dominates under low metal loading conditions, and another more abundant site that we term non-sulfhydryl sites that becomes important at high metal loadings. The resulting calculated stability constants do not vary significantly as a function of metal loading and yield reasonable fits to the observed adsorption behaviors as a function of both pH and metal loading. We use the results to calculate the speciation of metals bound by the bacterial envelope in realistic bacteria-bearing, heavy metal contaminated systems in order to demonstrate the potential importance of metal-sulfhydryl binding in the budget of bacterially-adsorbed metals under low metal-loading conditions.

Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: Isotherms, kinetics, thermodynamics and process mechanism.

PubMed

Badawi, M A; Negm, N A; Abou Kana, M T H; Hefni, H H; Abdel Moneem, M M

2017-06-01

Chitosan was reacted by tannic acid to obtain three modified chitosan biopolymer. Their chemical structures were characterized by FTIR and elemental analysis. The prepared biopolymers were used to adsorb Al(III) and Pb(II) metal ions from industrial wastewater. The factors affecting the adsorption process were biosorbent amount, initial concentration of metal ion and pH of the medium. The adsorption efficiency increased considerably with the increase of the biosorbent amount and pH of the medium. The adsorption process of biosorbent on different metal ions was fitted by Freundlich adsorption model. The adsorption kinetics was followed Pseudo-second-order kinetic model. The adsorption process occurred according to diffusion mechanism which was confirmed by the interparticle diffusion model. The modified biopolymers were efficient biosorbents for removal of Pb(II) and Al(III) metal ions from the medium. Copyright © 2017 Elsevier B.V. All rights reserved.

The analysis of heavy metal in leaching liquid of coal

NASA Astrophysics Data System (ADS)

Cao, Hongmei; Li, Guanglou; Zhang, Lu

2018-02-01

In this paper, heavy metals in coal were extracted by pure water to simulate the leaching effect of natural precipitation or artificial rainfall on outdoor storage of coal. The results show that the leaching liquid pH was slightly declining, and Cu, Zn, Pb, Cd were in μg/L level, far less than the hazardous waste identification standard of GB5085.3-2007. It suggests that leaching liquid was less harmful to environment when coal was immersed by big amount of water. In the case of spray or precipitation less, the pH drop was more obvious, leaching of heavy metals more, and the general elution of the initial dissolution of the most obvious. Although the amount of small but more toxic, the relevant management should be alert to its harmful.

Acidity and Alkalinity in mine drainage: Practical considerations

USGS Publications Warehouse

Cravotta, III, Charles A.; Kirby, Carl S.

2004-01-01

In this paper, we emphasize that the Standard Method hot peroxide treatment procedure for acidity determination (hot acidity) directly measures net acidity or net alkalinity, but that more than one water-quality measure can be useful as a measure of the severity of acid mine drainage. We demonstrate that the hot acidity is related to the pH, alkalinity, and dissolved concentrations of Fe, Mn, and Al in fresh mine drainage. We show that the hot acidity accurately indicates the potential for pH to decrease to acidic values after complete oxidation of Fe and Mn, and it indicates the excess alkalinity or that required for neutralization of the sample. We show that the hot acidity method gives consistent, interpretable results on fresh or aged samples. Regional data for mine-drainage quality in Pennsylvania indicated the pH of fresh samples was predominantly acidic (pH 2.5 to 4) or near neutral (pH 6 to 7); approximately 25 percent of the samples had intermediate pH values. This bimodal frequency distribution of pH was distinctive for fully oxidized samples; oxidized samples had acidic or near-neutral pH, only. Samples that had nearneutral pH after oxidation had negative hot acidity; samples that had acidic pH after oxidation had positive hot acidity. Samples with comparable pH values had variable hot acidities owing to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. The hot acidity was comparable to net acidity computed on the basis of initial pH and concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity computed from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was comparable to that computed on the basis of aqueous species and FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the hot acidities were comparable for fresh and aged samples. Thus, meaningful “net” acidity can be determined from a measured hot acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. Together, these water-quality data can be useful for evaluating the potential for toxicity, corrosion, or encrustation and can be helpful for determining the appropriate remediation. By demonstrating the measurements on fresh and aged samples, we hope to encourage (1) consistent use of the hot peroxide treatment procedure for acidity determination and (2) consistent reporting of negative acidity values.

Role of the Ca-pectates on the accumulation of heavy metals in the root apoplasm.

PubMed

Castaldi, Paola; Lauro, Giampaolo; Senette, Caterina; Deiana, Salvatore

2010-12-01

In order to better understand the processes that regulate the accumulation in the apoplasm of heavy metals and their mobilization by the plant metabolites it is essential to study the mechanisms that regulate the interactions between metal ions and pectins. In such a context, the sorption of Cd(II), Zn(II), Cu(II) and Pb(II) from single and multi-metal solutions, by a Ca-polygalacturonate gel with a degree of esterification of 18.0 (PGAM(1)) and 65.5% (PGAM(2)) was studied in the 3.0-6.0 pH range in the presence of CaCl(2) 2.5mM. The sorption of Cr(III) from single metal solution was also considered. The results show that the amount of each metal ion sorbed increases with increasing the initial metal ion concentration and pH. The data from the single metal solution tests show that at pH 6.0 the affinity of the metal ions towards the PGAM(1) matrix follows the order: Cr(III)>Cu(II)≅Pb(II)≫Zn(II)≅Cd(II). The simultaneous sorption of the bivalent metal ions by the PGAM(1) gels indicates that Pb(II) is selectively sorbed. The FT-IR spectra show that the carboxylate groups are mainly responsible for the metal ion coordination. The ability of PGAM(2) to accumulate Cr(III), Cu(II), and Pb(II) was lower than that found in the PGAM(1) systems whereas the sorption of Zn(II) and Cd(II) was negligible. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

Modeling the adsorption of metal ions (Cu 2+, Ni 2+, Pb 2+) onto ACCs using surface complexation models

NASA Astrophysics Data System (ADS)

Faur-Brasquet, Catherine; Reddad, Zacaria; Kadirvelu, Krishna; Le Cloirec, Pierre

2002-08-01

Activated carbon cloths (ACCs), whose efficiency has been demonstrated for microorganics adsorption from water, were here studied in the removal of metal ions from aqueous solution. Two ACCs are investigated, they are characterized in terms of porosity parameters (BET specific surface area, percentage of microporosity) and chemical characteristics (acidic surface groups, acidity constants, point of zero charge). A first part consists in the experimental study of three metal ions removal (Cu 2+, Ni 2+ and Pb 2+) in a batch reactor. Isotherms modeling by Freundlich and Brunauer-Emmett-Teller (BET) equations enables the following adsorption order: Cu 2+>Ni 2+>Pb 2+ to be determined for adsorption capacities on a molar basis. It may be related to adsorbates characteristics in terms of electronegativity and ionic radius. The influence of adsorbent's microporosity is also shown. Adsorption experiments carried out for pH values ranging from 2 to 10 demonstrate: (i) an adsorption occurring below the precipitation pH; (ii) the strong influence of pH, with a decrease of electrostatic repulsion due to the formation of less charged hydrolyzed species coupled with a decrease of activated carbon surface charge as pH increases. The second part focuses on the modeling of adsorption versus the pH experimental data by the diffuse layer model (DLM) using Fiteql software. The model is efficient to describe the system behavior in the pH range considered. Regarding complexation constants, they show the following affinity for ACC: Pb 2+>Cu 2+>Ni 2+. They are related to initial concentrations used for the three metal ions.

Weathering of historical copper slags in dynamic experimental system with rhizosphere-like organic acids.

PubMed

Potysz, Anna; Kierczak, Jakub; Grybos, Malgorzata; Pędziwiatr, Artur; van Hullebusch, Eric D

2018-06-01

This study was undertaken to simulate experimentally the weathering of slags disposed nearby soil rhizosphere. The aim of the research was to differentiate the effect of pH and organics on slags dissolution as well as to indicate weathering sequence of phase components. The studied slags are mainly composed of Fe (34.5 wt%) and Si (17.9 wt%) and contain up to 3761 mg kg -1 of Cu and 3628 mg kg -1 of Zn. The main identified phases are fayalite and glass, whereas sulfides and metallic Cu are volumetrically minor. A 30 days long slag weathering experiment was carried out with artificial root exudates (43.7 mM) and demineralized water at initial pH = 3.5 and pH = 6.7. The highest metal release (up to 10.9% of Zn and 4.6% of Cu) was observed in ARE solution at initial pH 3.5. Dissolution of sulfides and fayalite was mainly driven by pH. Artificial root exudates enhance glass dissolution as compared to demineralized water regardless of initially fixed pH. Based on this study following weathering sequences are delineated: i) under ARE 3.5 conditions: silicates > glass > sulfides, ii) under DW 3.5 conditions: sulfides > silicates > glass, iii) under near-neutral conditions: sulfides > glass > silicates. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metal mobilization from metallurgical wastes by soil organic acids.

PubMed

Potysz, Anna; Grybos, Malgorzata; Kierczak, Jakub; Guibaud, Gilles; Fondaneche, Patrice; Lens, Piet N L; van Hullebusch, Eric D

2017-07-01

Three types of Cu-slags differing in chemical and mineralogical composition (historical, shaft furnace, and granulated slags) and a matte from a lead recovery process were studied with respect to their susceptibility to release Cu, Zn and Pb upon exposure to organic acids commonly encountered in soil environments. Leaching experiments (24-960 h) were conducted with: i) humic acid (20 mg/L) at pH t 0  = 4.4, ii) fulvic acid (20 mg/L) at pH t 0  = 4.4, iii) an artificial root exudates (ARE) (17.4 g/L) solution at pH t 0  = 4.4, iv) ARE solution at pH t 0  = 2.9 and v) ultrapure water (pH t 0  = 5.6). The results demonstrated that the ARE contribute the most to the mobilization of metals from all the wastes analyzed, regardless of the initial pH of the solution. For example, up to 14%, 30%, 24% and 5% of Cu is released within 960 h from historical, shaft furnace, granulated slags and lead matte, respectively, when exposed to the artificial root exudates solution (pH 2.9). Humic and fulvic acids were found to have a higher impact on granulated and shaft furnace slags as compared to the ultrapure water control and increased the release of metals by a factor up to 37.5 (Pb) and 20.5 (Cu) for granulated and shaft furnace slags, respectively. Humic and fulvic acids amplified the mobilization of metals by a maximal factor of 13.6 (Pb) and 12.1 (Pb) for historical slag and lead matte, respectively. The studied organic compounds contributed to different release rates of metallic contaminants from individual metallurgical wastes under the conditions tested. Copyright © 2017 Elsevier Ltd. All rights reserved.

The use of raw and acid-pretreated bivalve mollusk shells to remove metals from aqueous solutions.

PubMed

Liu, Yang; Sun, Changbin; Xu, Jin; Li, Youzhi

2009-08-30

Heavy metal removal from industrial wastewater is not only to protect living organisms in the environment but also to conserve resources such as metals and water by enabling their reuse. To overcome the disadvantage of high cost and secondary pollution by the conventional physico-chemical treatment techniques, environmentally benign and low-cost adsorbents are in demand. In this study, the use of raw and acid-pretreated bivalve mollusk shells (BMSs) to remove metals from aqueous solutions with single or mixed metal was evaluated at different BMSs doses, pH and temperatures in batch shaking experiments in laboratory conditions. When the BMSs were used to treat CuSO(4)x5H(2)O solution, the copper sorption capacities of the raw and acid-pretreated BMSs were approximately 38.93 mg/g and 138.95 mg/g, respectively. The copper removal efficiency (CRE) of the raw BMSs became greatly enhanced with increasing initial pH, reaching 99.51% at the initial pH 5. Conversely, the CRE of the acid-pretreated BMSs was maintained at 99.48-99.52% throughout the pH range of 1-5. Furthermore, the CRE values of the raw and acid-pretreated BMSs were not greatly changed when the temperature was varied from 15 degrees C to 40 degrees C. In addition, the CRE value of the raw BMSs was maintained for 12 cycles of sorption-desorption with a CRE of 98.4% being observed in the final cycle. Finally, when the BMSs were used to treat electroplating wastewater, the removal efficiencies (REs) of the raw BMSs were 99.97%, 98.99% and 87% for Fe, Zn and Cu, respectively, whereas the REs of the acid-pretreated BMSs were 99.98%, 99.43% and 92.13%, respectively. Ion exchange experiments revealed that one of mechanisms for metal sorption by the BMSs from aqueous solution is related to ion exchange, especially between the metal ions in the treated solution and Ca(2+) from BMSs. Infrared absorbance spectra analysis indicated that the acid pretreatment led to occurrence of the groups (i.e. -OH, -NH, C=O and S=O) of negative charge in treated BMSs. Scanning electron microscopy revealed that acid pretreatment enabled the used BMSs to form the flake-shaped structure with smooth surfaces that can supply a better interface for binding metal ions.

Redox Deposition of Nanoscale Metal Oxides on Carbon for Next-Generation Electrochemical Capacitors

DTIC Science & Technology

2013-01-01

Nanoscale Metal Oxides Sassin et al. Redox Deposition Approaches to Nanoscale Coatings of Metal Oxides Manganese Oxides. Permanganate (MnO4 ) is a versa...scalability of the permanganate carbon redox reaction for generating MnOx coatings that store charge.21 The initial study per- formed on planar graphite...the carbon surface from the aqueous permanganate solu- tion (pH∼5),29,35 evidenced by a sharp increase in solution pH and a decrease in solution

Catalytic decomposition of toxic chemicals over iron group metals supported on carbon nanotubes.

PubMed

Li, Lili; Chen, Can; Chen, Long; Zhu, Zixue; Hu, Jianli

2014-03-18

This study explores catalytic decomposition of phosphine (PH3) using iron group metals (Co, Ni) and metal oxides (Fe2O3, Co(3)O4, NiO) supported on carbon nanotubes (CNTs). The catalysts are synthesized by means of a deposition-precipitation method. The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations, including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in the PH3 decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that phosphidation occurs on the catalyst surface, and the resulting metal phosphides act as an active phase in the PH3 decomposition reaction. Cobalt phosphide, CoP, is formed on Co/CNTs and Co(3)O4/CNTs, whereas iron phosphide, FeP, is formed on Fe2O3/CNTs. In contrast, phosphorus-rich phosphide NiP2 is formed on Ni/CNTs and NiO/CNTs. The initial activities of the catalysts are shown in the following sequence: Ni/CNTs > Co/CNTs > Co(3)O4/CNTs >NiO/CNTs > Fe2O3/CNTs, whereas activities of metal phosphides are shown in the following order: CoP > NiP2 > FeP. The catalytic activity of metal phosphides is attributed to their electronic properties. Cobalt phosphide formed on Co/CNTs and Co(3)O4/CNTs exhibits not only the highest activity, but also long-term stability in the PH3 decomposition reaction.

Prediction of equilibrium parameters of adsorption of lead (II) ions onto diatomite

NASA Astrophysics Data System (ADS)

Salman, Taylan; Ardalı, Yüksel; Gamze Turan, N.

2013-04-01

Heavy metals from industrial wastewaters are one of the most important environmental issues to be solved today. Due to their toxicity and nonbiodegradable nature, heavy metals cause environmental and public health problems. Various techniques have been developed to remove heavy metals from aqueous solutions. These include chemical precipitation, reverse osmosis, ion Exchange and adsorption. Among them, adsorption is considered to be a particularly competitive and effective process for the removal of heavy metals from aqueous solutions. There is growing interest in using low cost, commercially available materials for the adsorption of heavy metals. Diatomite is a siliceous sedimentary rock having an amorphous form of silica (SiO2. nH2O) containing a small amount of microcrystalline material. It has unique combination of physical and chemical properties such as high porosity, high permeability, small particle size, large surface area, and low thermal conductivity. In addition, it is available in Turkey and in various locations around the world. Therefore, diatomite has been successfully used as adsorbent for the removal of heavy metals. The aim of the study is to investigate the adsorption properties of diatomite. The equilibrium adsorption data were applied to the Langmuir, Freundlich and Dubinin-Radushkevic (D-R) isotherm models. Adsorption experiments were performed under batch process, using Pb (II) initial concentration, pH of solution and contact time as variables. The results demonstrated that the adsorption of Pb (II) was strongly dependent on pH of solution. The effect of pH on adsorption of Pb(II) on diatomite was conducted by varying pH from 2 to 12 at 20 oC. In the pH range of 2.0-4.0, the adsorption percentage increases slightly as the pH increasing. At pH>4, the adsorption percentage decreases with increasing pH because hydrolysis product and the precipitation begin to play an important role in the sorption of Pb (II). At pH4, the maximum adsorption capacity of diatomite was found as 26.158 mg/g. The adsorption isotherms of Pb (II) on diatomite can be described well by the Freundlich model. The high adsorption capacity of diatomite makes it suitable low-cost material in the removal of Pb (II) from aqueous solutions.

Equilibrium and kinetic modelling of chromium(III) sorption by animal bones.

PubMed

Chojnacka, Katarzyna

2005-04-01

The paper discusses sorption of Cr(III) ions from aqueous solutions by animal bones. Animal bones were found to be an efficient sorbent with the maximum experimentally determined sorption capacity in the range 29-194 mg g(-1) that depended on pH and temperature. The maximum experimentally determined sorption capacity was obtained at 50 degrees C, pH 5. Batch kinetics and equilibrium experiments were performed in order to investigate the influence of contact time, initial concentration of sorbate and sorbent, temperature and pH. It was found that sorption capacity increased with increase of Cr(III) concentration, temperature and initial pH of metal solution. Mathematical models describing kinetics and statics of sorption were proposed. It was found that process kinetics followed the pseudo-second-order pattern. The influence of sorbent concentration was described with Langmuir-type equation and the influence of sorbate concentration was described with empirical dependence. The models were positively verified.

Removal of bisphenol A and some heavy metal ions by polydivinylbenzene magnetic latex particles.

PubMed

Marzougui, Zied; Chaabouni, Amel; Elleuch, Boubaker; Elaissari, Abdelhamid

2016-08-01

In this study, magnetic polydivinylbenzene latex particles MPDVB with a core-shell structure were tested for the removal of bisphenol A (BPA), copper Cu(II), lead Pb(II), and zinc Zn(II) from aqueous solutions by a batch-adsorption technique. The effect of different parameters, such as initial concentration of pollutant, contact time, adsorbent dose, and initial pH solution on the adsorption of the different adsorbates considered was investigated. The adsorption of BPA, Cu(II), Pb(II), and Zn(II) was found to be fast, and the equilibrium was achieved within 30 min. The pH 5-5.5 was found to be the most suitable pH for metal removal. The presence of electrolytes and their increasing concentration reduced the metal adsorption capacity of the adsorbent. Whereas, the optimal pH for BPA adsorption was found 7, both hydrogen bonds and π-π interaction were thought responsible for the adsorption of BPA on MPDVB. The adsorption kinetics of BPA, Cu(II), Pb(II), and Zn(II) were found to follow a pseudo-second-order kinetic model. Equilibrium data for BPA, Cu(II), Pb(II), and Zn(II) adsorption were fitted well by the Langmuir isotherm model. Furthermore, the desorption and regeneration studies have proven that MPDVB can be employed repeatedly without impacting its adsorption capacity.

Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures

DOEpatents

Adzic, Radoslav R.; Harris, Alexander

2015-10-06

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The manufacturing process may involve initial oxidation of the carbon nanostructures followed by immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means and the nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. Subsequent film growth may be performed via the initial quasi-underpotential deposition of a non-noble metal followed by immersion in a solution comprising a more noble metal. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures

DOEpatents

Adzic, Radoslav; Harris, Alexander

2013-03-26

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means and the nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. Subsequent film growth may be performed via the initial quasi-underpotential deposition of a non-noble metal followed by immersion in a solution comprising a more noble metal. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

The kinetic and mechanical aspects of hydrogen-induced failure in metals. Ph.D. Thesis, 1971

NASA Technical Reports Server (NTRS)

Nelson, H. G.

1972-01-01

Premature hydrogen-induced failure observed to occur in many metal systems involves three stages of fracture: (1) crack initiation, (2) stable slow crack growth, and (3) unstable rapid crack growth. The presence of hydrogen at some critical location on the metal surface or within the metal lattice was shown to influence one or both of the first two stages of brittle fracture but has a negligible effect on the unstable rapid crack growth stage. The relative influence of the applied parameters of time, temperature, etc., on the propensity of a metal to exhibit hydrogen induced premature failure was investigated.

Aging of coprecipitated Cu in alumina: changes in structural location, chemical form, and solubility

NASA Astrophysics Data System (ADS)

Martínez, Carmen Enid; McBride, Murray B.

2000-05-01

The longterm fate of metals in mineral solid phases is not well established, as aging effects can alter metal forms and solubility. We use a model system (Cu coprecipitation with alumina) to examine copper solubility, chemical form, and structural location during longterm aging (up to 2 y), and as a function of Cu concentration, suspension pH, and rate of coprecipitate formation. Electron spin resonance (ESR) spectroscopy and extractability with EDTA were used to determine the chemical form and structural location of Cu in coprecipitates with alumina. Soluble Cu was measured by differential pulse anodic stripping voltammetry (dpasv) and alumina transformation monitored by XRD. Decreased Cu solubility resulted after prolonged aging of the coprecipitates formed at pH 6 and pH 7.5. Longterm aging (up to 2 y at 23°C) induced the transformation of an initially noncrystalline alumina to more ordered products including gibbsite. Results obtained by ESR and EDTA extraction indicate Cu movement towards the surface of the coprecipitate at increased aging time. Copper was initially evenly distributed within the alumina, but segregated at or near the alumina surface forming CuO and/or clusters after longterm reaction (2 y) with alumina.

Copper, lead and zinc removal from metal-contaminated wastewater by adsorption onto agricultural wastes.

PubMed

Janyasuthiwong, Suthee; Phiri, Sheila M; Kijjanapanich, Pimluck; Rene, Eldon R; Esposito, Giovanni; Lens, Piet N L

2015-01-01

The use of agricultural wastes (groundnut shell, orange and banana peel, rice husk, coconut husk and Wawa tree saw dust) as potential cost-effective adsorbent for heavy metal removal from wastewater was evaluated. The effect of pH (2.0-6.0), adsorbent dosage (0.6-2.2 g), contact time (10-130 min) and initial concentration (Pb: 5-105 mg/L, Cu and Zn: 2.5-52.7 mg/L) on the metal removal efficiency and uptake capacity were investigated using response surface methodology to optimize the process conditions. Groundnut shell showed a high potential to remove Cu, Pb and Zn from synthetic wastewater. The highest removal efficiencies with groundnut as the adsorbent were 85% at pH 5.0 for Cu and 98% at pH 3.0 for Pb and Zn. The optimum conditions obtained were 2.5 g adsorbent with 40.7 mg/L Cu at pH 4.4 and 64 min contact time, 2.5 g adsorbent with 196.1 mg/L Pb at pH 5.6 and 60 min contact time and 3.1 g adsorbent with 70.2 mg/L Zn at pH 4.3 and 50 min contact time, for Cu, Pb and Zn, respectively. The regeneration of the groundnut shell was possible for a maximum of three cycles using 0.2 M HCl as the desorbing solution without any significant change in the adsorbing efficiency.

Removal of Manganese from Solution using Polyamide Membrane

NASA Astrophysics Data System (ADS)

Mathaba, M.; Sithole, N.; Mashifana, T.

2018-03-01

The work demonstrates the performance of polyamide membrane in the removal of manganese ions from single salt aqueous solution simulating real acid mine drainage. The membrane was tested using a dead-end filtration cell with manganese sulphate was used to prepare a feed solution. The membrane flux and metal rejection was evaluated. Effect of operating parameters such as pH, initial feed concentration and pressure on membrane performance was investigated. The pressure was varied between 10 and 15 bar and it was observed that increasing the pressure increases the membrane flux. Acidic pH conditions contributed to the removal of the contaminate as Mn2+ ions are freely at low pH. The percentage rejection was found to be 63.5 to 77.6 % as concentration is increased from 290 ppm to 321 ppm for a feed solution. The membrane showed satisfactory results in removing metal ions from solution.

Effects of Metals Associated with Wildfire Ash on Water Quality

NASA Astrophysics Data System (ADS)

Cerrato, J.; Clark, A.; Correa, N.; Ali, A.; Blake, J.; Bixby, R.

2015-12-01

The forests of the western United States are impacted dramatically by climate change and have suffered from large-scale increases in wildfire activity. This rise in wildfires introduces additional ash to ecosystems and can represent a serious and ongoing threat to water quality in streams and rivers from storm event runoff in burn areas. The effect of metals associated with wildfire ash (from wood collected from the Valles Caldera National Preserve, Jemez Mountains, New Mexico) on solution pH and dissolved oxygen was assessed through a series of laboratory experiments. Microscopy and spectroscopy analyses were conducted to characterize the elemental content and oxidation state of metals in unreacted and reacted ash. Certain metals (e.g., Ca, K, Al, Mg) were detected in ash from ponderosa pine, one of the dominant species in the Valles Caldera, with mean concentrations ranging from 400-1750 mg kg-1. Other metals (e.g., Na, Fe, Mn, V, Zn, Ni) were present at lower mean concentrations ranging from 12-210 mg kg-1. The initial pH after conducting batch experiments reacting ash with water started at 9.9 and the alkalinity of the water was 110 mg L-1 as CaCO3. Solution pH decreased to 8.0 after 48 hours of reaction, which is almost a delta of two pH units. Dissolved oxygen concentrations decreased by 2 mg L-1 over the course of 12 hours before the rate of reaeration surpassed the rate of consumption. This presentation will discuss how redox-active metals, such as Fe and Mn, could contribute to the increased dissolved oxygen demand and fluctuation of the oxidation/reduction potential in the system.

Changes in lead and zinc lability during weathering-induced acidification of desert mine tailings: Coupling chemical and micro-scale analyses.

PubMed

Hayes, Sarah M; White, Scott A; Thompson, Thomas L; Maier, Raina M; Chorover, Jon

2009-12-01

Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5 to 8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and "bioavailable" metal concentrations result from associated variation in particle-scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 - 13 g kg(-1)) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4 - 6 g kg(-1)) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools.

Changes in lead and zinc lability during weathering-induced acidification of desert mine tailings: Coupling chemical and micro-scale analyses

PubMed Central

Hayes, Sarah M.; White, Scott A.; Thompson, Thomas L.; Maier, Raina M.; Chorover, Jon

2009-01-01

Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5 to 8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and “bioavailable” metal concentrations result from associated variation in particle-scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 – 13 g kg−1) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4 – 6 g kg−1) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools. PMID:20161492

Highly selective biaryl cross-coupling reactions between aryl halides and aryl Grignard reagents: a new catalyst combination of N-heterocyclic carbenes and iron, cobalt, and nickel fluorides.

PubMed

Hatakeyama, Takuji; Hashimoto, Sigma; Ishizuka, Kentaro; Nakamura, Masaharu

2009-08-26

Combinations of N-heterocyclic carbenes (NHCs) and fluoride salts of the iron-group metals (Fe, Co, and Ni) have been shown to be excellent catalysts for the cross-coupling reactions of aryl Grignard reagents (Ar(1)MgBr) with aryl and heteroaryl halides (Ar(2)X) to give unsymmetrical biaryls (Ar(1)-Ar(2)). Iron fluorides in combination with SIPr, a saturated NHC ligand, catalyze the biaryl cross-coupling between various aryl chlorides and aryl Grignard reagents in high yield and high selectivity. On the other hand, cobalt and nickel fluorides in combination with IPr, an unsaturated NHC ligand, exhibit interesting complementary reactivity in the coupling of aryl bromides or iodides; in contrast, with these substrates the iron catalysts show a lower selectivity. The formation of homocoupling byproducts is suppressed markedly to less than 5% in most cases by choosing the appropriate metal fluoride/NHC combination. The present catalyst combinations offer several synthetic advantages over existing methods: practical synthesis of a broad range of unsymmetrical biaryls without the use of palladium catalysts and phosphine ligands. On the basis of stoichiometric control experiments and theoretical studies, the origin of the unique catalytic effect of the fluoride counterion can be ascribed to the formation of a higher-valent heteroleptic metalate [Ar(1)MF(2)]MgBr as the key intermediate in our proposed catalytic cycle. First, stoichiometric control experiments revealed the stark differences in chemical reactivity between the metal fluorides and metal chlorides. Second, DFT calculations indicate that the initial reduction of di- or trivalent metal fluoride in the wake of transmetalation with PhMgCl is energetically unfavorable and that formation of a divalent heteroleptic metalate complex, [PhMF(2)]MgCl (M = Fe, Co, Ni), is dominant in the metal fluoride system. The heteroleptic ate-complex serves as a key reactive intermediate, which undergoes oxidative addition with PhCl and releases the biaryl cross-coupling product Ph-Ph with reasonable energy barriers. The present cross-coupling reaction catalyzed by iron-group metal fluorides and an NHC ligand provides a highly selective and practical method for the synthesis of unsymmetrical biaryls as well as the opportunity to gain new mechanistic insights into the metal-catalyzed cross-coupling reactions.

Biosorption of Zn(II) from industrial effluents using sugar beet pulp and F. vesiculosus: From laboratory tests to a pilot approach.

PubMed

Castro, Laura; Blázquez, M Luisa; González, Felisa; Muñoz, Jesús A; Ballester, Antonio

2017-11-15

The aim of this work was to demonstrate the feasibility of the application of biosorption in the treatment of metal polluted wastewaters through the development of several pilot plants to be implemented by the industry. The use as biosorbents of both the brown seaweed Fucus vesiculosus and a sugar beet pulp was investigated to remove heavy metal ions from a wastewater generated in an electroplating industry: Industrial Goñabe (Valladolid, Spain). Batch experiments were performed to study the effects of pH, contact time and initial metal concentration on metal biosorption. It was observed that the adsorption capacity of the biosorbents strongly depended on the pH, increasing as the pH rises from 2 to 5. The adsorption kinetic was studied using three models: pseudo first order, pseudo second order and Elovich models. The experimental data were fitted to Langmuir and Freundlich isotherm models and the brown alga F. vesiculosus showed higher metal uptake than the sugar beet pulp. The biomasses were also used for zinc removal in fixed-bed columns. The performance of the system was evaluated in different experimental conditions. The mixture of the two biomasses, the use of serial columns and the inverse flow can be interesting attempts to improve the biosorption process for large-scale applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption of Cu2+ to biomass ash and its modified product.

PubMed

Xu, Lei; Cui, Hongbiao; Zheng, Xuebo; Liang, Jiani; Xing, Xiangyu; Yao, Lunguang; Chen, Zhaojin; Zhou, Jing

2017-04-01

Ash produced by biomass power plants has great potential for the removal of heavy metal ions from aqueous solution. The pollution of toxic heavy metals to water is a worldwide environmental problem. Discharges containing copper, in particular, are strictly controlled because the excessive copper can cause serious harm to the environment and human health. This work aims to investigate the adsorption characteristics of copper ions in aqueous solution by biomass ash and the modified products, and to evaluate their potential application in water pollution control. The biomass ash was modified with a mesoporous siliceous material and functionalized with 3-aminopropyltriethoxysilane. The surface properties of the biomass ash and the new matrix were studied to evaluate their adsorption property for Cu 2+ ions at different pHs, initial metal concentrations and the thermodynamic and kinetic were studied. The chemical and morphological properties of this modified material are analyzed; the specific surface area of the modified biomass ash was nine times that of the initial ash. Both of the two materials showed a strong affinity for Cu 2+ , and the Langmuir model could best represent the adsorption characteristics of Cu 2+ on the two kinds of materials. The adsorption capacity of copper on the material increased with the increase of pH and pH 6 was the optimum pH. Thermodynamic analysis results showed that the adsorption of Cu 2+ was spontaneous and endothermic in nature. The adsorptions of Cu 2+ onto the modified biomass ash followed pseudo-second-order kinetics.

Removal of Mn(II) from the acid mine wastewaters using coal fired bottom ash

NASA Astrophysics Data System (ADS)

Mahidin, M.; Sulaiman, T. N.; Muslim, A.; Gani, A.

2017-06-01

Acid mine wastewater (AMW), the wastewater from mining activities which has low pH about 3-5 and contains hazardous heavy metals such as Cu, Fe, Mn, Zn, Pb, etc. Those heavy metals pollution is of prime concern from the environmental view point. Among the heavy metals, Mn occupies the third position in the AMW from one the iron ore mining company in Aceh, Indonesia. In this study, the possibility use of bottom ash from coal fired boiler of steam power plants for the removal of Mn(II) in AMW has been investigated. Experimental has been conducted as follows. Activation of bottom ash was done both by physical and chemical treatments through heating at 270 °C and washing with NaOH activator 0.5 and 1 M. Adsorption test contains two parts observation; preliminary and primary experiments. Preliminary study is addressed to select the best condition of three independent variables i.e.: pH of AMW (3 & 7), bottom ash particle size (40, 60 & 100 mesh) and initial Mn(II) concentrations (100 & 600 mg/l). AMW used was synthetics wastewater. It was found that the best value for NaOH is 1 M, pH is 7, particle size is 100 meshes and initial Mn(II) concentration is 600 mg/l from the adsorption efficiency point of view. The maximum adsorption capacity (q e) is 63.7 mg/g with the efficiency of 85%.

Bioremediation of uranium-bearing wastewater: Biochemical and chemical factors influencing bioprocess application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Macaskie, L.E.; Yong, P.; Doyle, T.C.

1997-01-05

A biotechnological process for the removal of heavy metals from aqueous solution utilizes enzymatically liberated phosphate ligand which precipitates with heavy metals (M) as cell-bound MHPO{sub 4}. The enzyme, a phosphatase, obeys Michaelis-Menten kinetics in resting and immobilized cells; an integrated form of the Michaelis-Menten equation was used to calculate the apparent K{sub m} (K{sub m app}) as operating in immobilized cells in flow-through columns by a ratio method based on the use of two enzyme loadings (E{sub o1}, E{sub o2}) or two input substrate concentrations (S{sub o1}, S{sub o2}). The calculated K{sub m app} (4.08 mM) was substituted intomore » an equation to describe the removal of metals by immobilized cells. In operation the activity of the bioreactor was in accordance with that predicted mathematically, within 10%. The initial tests were done at neutral pH, whereas the pH of industrial wastewaters is often low; an increase in the K{sub m app} at low pH was found in previous studies. Immobilized cells were challenged with acidic mine drainage wastewaters, where the limiting factors were chemical and not biochemical. Bioreactors initially lost activity in this water, but recovered to remove uranyl ion with more than 70% efficiency under steady-state conditions in the presence of competing cations and anions. Possible reasons for the bioreactor recovery are chemical crystallization factors.« less

Adsorption of Hg(II) and Pb(II) ions by nanoscale zero valent iron supported on ostrich bone ash in a fixed-bed column system.

PubMed

Amiri, Mohammad Javad; Abedi-Koupai, Jahangir; Eslamian, Saeid

2017-07-01

In this research, ostrich bone ash (OBA) was modified with nanoscale zerovalent iron (nZVI) particles and applied as a novel composite adsorbent (OBA/nZVI) for dynamic adsorption/reduction of Hg(II) and Pb(II) ions in a fixed-bed column system. Entrapment of nZVI in OBA beads barricades the particles from oxidation and aggregation. The dynamic behavior of metal ions removal by OBA/nZVI was assessed as a function of inlet flow rates, bed height, initial pollutants concentration and pH. The synthesized OBA/nZVI composite was characterized by several physicochemical techniques. Increase in pH and bed height and decrease in flow rates and initial metal concentration resulted in delay of breakthrough time. OBA breakthrough profile is sharper than the OBA/nZVI breakthrough curve for both metal ions and the breakthrough times increase in the order OBA/nZVI-Hg(II) > OBA/nZVI-Pb(II) > OBA-Pb(II) > OBA-Hg(II). Based on the experiment results, redox reaction is expected to occur to a certain extent, as the standard reduction potentials of Hg(II) and Pb(II) are more than that of Fe(II). From a practical point of view, the OBA/nZVI could be applied as a material to remove Hg(II) and Pb(II) ions from natural surface and ground water with a pH value of 5-9.

A comparison of three electrodes for the measurement of pH in small volumes.

PubMed

Smit, A; Pollard, M; Cleaton-Jones, P; Preston, A

1997-01-01

An ion-sensitive field effect transistor (ISFET, Sentron, Sentron, Inc.) electrode was compared with a glass combination micro-electrode (MI-410, Micro-electrodes, Inc.) and a solid-state metal wire oxide pH sensor (Beetrode, World Precision Instruments, Inc.) with a liquid junction reference electrode (MERE1, World Precision Instruments, Inc.). The electrodes were assessed for linearity, reproducibility, accuracy, drift from the initial calibration between pH 4 and pH 7 and the time taken to record a stable reading. The ISFET was used to determine the pH in dental plaque samples (1 mg suspended in 20 microliters). The pH values correlated with the hydrogen ion concentration for all the electrodes (r = 0.98). The MI-410 fractured before this evaluation was completed. Coefficients of variation were 0.65% (pH 4) and 0.08% (pH 7) for the ISFET and 4.69% (pH 4) and 3.46% (pH 7) for the Beetrode. Both electrodes gave readings that differed significantly from the initial calibration, but the drift was greater for the Beetrode (F = 7.93; p = 0.0005) than the ISFET (F = 1.89; p = 0.1519). However, this drift was smaller than the change in pH as measured in dental plaque samples. The Beetrode gave a stable reading after 3.39 +/- 0.83 s and the ISFET after 2.2 +/- 0.76 s, while the MI-410 required at least 20 s. The ISFET type electrode is suitable for use in small volumes such as plaque suspensions, is easier to operate and yields results closer to the initial calibration than the Beetrode and is more robust than the MI-410 and the Beetrode.

Mechanistic study of lead desorption during the leaching process of ion-absorbed rare earths: pH effect and the column experiment

NASA Astrophysics Data System (ADS)

Xue, Q.; Tang, J., Sr.; Chen, H.

2017-12-01

High concentrations of ammonium sulfate, often used in the in-situ mining process, can result in a decrease of pH in the environment and dissolution of rare earth metals. Ammonium sulfate can also cause desorption of toxic heavy metals, leading to environmental and human health implications. In this study, the desorption behavior and fraction changes of lead in the ion-absorbed rare earth ore were studied using batch desorption experiments and column leaching tests. Results from batch desorption experiments showed that the desorption process of lead included fast and slow stages, and followed an Elovich model well. The desorption rate and the proportion of lead content in the solution to the total lead in the soil were observed to increase with a decrease in the initial pH of the ammonium sulfate solution. The lead in soil included an acid extractable fraction, reducible fraction, oxidizable fraction, and a residual fraction, with the predominant fractions being the reducible and acid extractable fractions. 96% of the extractable fraction in soil were desorbed into solution at pH=3.0, and the content of the reducible fraction was observed to initially increase (when pH>4.0) and then decrease (when pH<4.0) with a decrease in pH. Column leaching tests indicated that the content of lead in the different fractions of soil followed the trend of reducible fraction > oxidizable fraction > acid extractable fraction > residual fraction after the simulating leaching mining process. The change in pH was also found to have a larger influence on the acid extractable and reducible fractions than the other two fractions. The proportion of the extractable fraction being leached was ca. 86%, and the reducible fraction was enriched along the migration direction of the leaching liquid. These results suggest that certain lead fractions may desorb again and contaminate the environment via acid rain, which provides significant information for environmental assessment and remediation after mining process.

Tartrazine modified activated carbon for the removal of Pb(II), Cd(II) and Cr(III).

PubMed

Monser, Lotfi; Adhoum, Nafaâ

2009-01-15

A two in one attempt for the removal of tartrazine and metal ions on activated carbon has been developed. The method was based on the modification of activated carbon with tartrazine then its application for the removal of Pb(II), Cd(II) and Cr(III) ions at different pH values. Tartrazine adsorption data were modelled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacities qm were 121.3, 67 and 56.7mgg(-1) at initial pH values of 1.0, 6.0 and 10, respectively. The adsorption of tartrazine onto activated carbon followed second-order kinetic model. The equilibrium time was found to be 240min at pH 1.0 and 120min at pH 10 for 500mgL(-1) tartrazine concentration. A maximum removal of 85% was obtained after 1h of contact time. The presence of tartrazine as modifier enhances attractive electrostatic interactions between metal ions and carbon surface. The adsorption capacity for Pb(II), Cd(II) and Cr(III) ions has been improved with respect to non-modified carbon reaching a maximum of 140%. The adsorption capacity was found to be a pH dependent for both modified and non-modified carbon with a greater adsorption at higher pH values except for Cr(III). The enhancement percent of Pb(II), Cd(II) and Cr(III) at different pH values was varied from 28% to 140% with respect to non-modified carbon. The amount of metal ions adsorbed using static regime was 11-40% higher than that with dynamic mode. The difference between adsorption capacities could be attributed to the applied flow rate.

Thermodynamic and kinetic studies of biosorption of iron and manganese from aqueous medium using rice husk ash

NASA Astrophysics Data System (ADS)

Adekola, F. A.; Hodonou, D. S. S.; Adegoke, H. I.

2016-11-01

The adsorption behavior of rice husk ash with respect to manganese and iron has been studied by batch methods to consider its application for water and waste water treatment. The optimum conditions of adsorption were determined by investigating the effect of initial metal ion concentration, contact time, adsorbent dose, pH value of aqueous solution and temperature. Adsorption equilibrium time was observed at 120 min. The adsorption efficiencies were found to be pH dependent. The equilibrium adsorption experimental data were found to fit the Langmuir, Freundlich and Temkin isotherms for iron, but fitted only Langmuir isotherm for manganese. The pseudo-second order kinetic model was found to describe the manganese and iron kinetics more effectively. The thermodynamic experiment revealed that the adsorption processes involving both metals were exothermic. The adsorbent was finally applied to typical raw water with initial manganese and iron concentrations of 3.38 mg/l for Fe and 6.28 mg/l, respectively, and the removal efficiency was 100 % for Mn and 70 % for Fe. The metal ions were desorbed from the adsorbent using 0.01 M HCl, it was found to quantitatively remove 67 and 86 % of Mn and Fe, respectively, within 2 h. The results revealed that manganese and iron are considerably adsorbed on the adsorbent and could be an economic method for the removal of these metals from aqueous solutions.

The Relationship between TOC and pH with Exchangeable Heavy Metal Levels in Lithuanian Podzols

NASA Astrophysics Data System (ADS)

Khaledian, Yones; Pereira, Paulo; Brevik, Eric C.; Pundyte, Neringa; Paliulis, Dainius

2017-04-01

Heavy metals can have a negative impact on public and environmental health. The objective of this study was to investigate the relationship between total organic carbon (TOC) and pH with exchangeable heavy metals (Pb, Cd, Cu and Zn) in order to predict exchangeable heavy metal content in soils sampled near Panevėžys and Kaunas, Lithuania. Principal component regression (PCR) and nonlinear regression methods were tested to find the statistical relationship between TOC and pH with heavy metals. The results of PCR [R2 = 0.68, RMSE = 0.07] and non-linear regression [R2 = 0.74, RMSE= 0.065] (pH with TOC and exchangeable parameters) were statistically significant. However, this was not observed in the relationships of pH and TOC separately with exchangeable heavy metals. The results indicated that pH had a higher correlation with exchangeable heavy metals (non-linear regression [R2 = 0.72, RMSE= 0.066]) than TOC with heavy metals [R2 = 0.30, RMSE= 0.004]. It can be concluded that even though there was a strong relationship between TOC and pH with exchangeable metals, the metal mobility (exchangeable metals) can be explained by pH better than TOC in this study. Finally, manipulating soil pH could likely be productive to assess and control heavy metals when financial and time limitations exist (Khaledian et al. 2016). Reference(s) Khaledian Y, Pereira P, Brevik E.C, Pundyte N, Paliulis D. 2016. The Influence of Organic Carbon and pH on Heavy Metals, Potassium, and Magnesium Levels in Lithuanian Podzols. Land Degradation and Development. DOI: 10.1002/ldr.2638

Formation of Manganese Oxide Coatings onto Sand for Adsorption of Trace Metals from Groundwater.

PubMed

Tilak, A S; Ojewole, S; Williford, C W; Fox, G A; Sobecki, T M; Larson, S L

2013-11-01

Manganese oxide (MnO) occurs naturally in soil and has a high affinity for trace metals adsorption. In this work, we quantified the factors (pH; flow rate; use of oxidants such as bleach, HO, and O; initial Mn(II) concentrations; and two types of geologic media) affecting MnO coatings onto Ottawa and aquifer sand using batch and column experiments. The batch experiments consisted of manual and automated titration, and the column experiments mimicked natural MnO adsorption and oxidation cycles as a strategy for in situ adsorption. A Pb solution of 50 mg L was passed through MnO-coated sand at a flow rate of 4 mL min to determine its adsorption capacity. Batch experimental results showed that MnO coatings increased from pH 6 to 8, with maximum MnO coating occurring at pH 8. Regarding MnO coatings, bleach and O were highly effective compared with HO. The Ottawa sand had approximately twice the MnO coating of aquifer sand. The sequential increase in initial Mn(II) concentrations on both sands resulted in incremental buildup of MnO. The automated procedure enhanced MnO coatings by 3.5 times compared with manual batch experiments. Column results showed that MnO coatings were highly dependent on initial Mn(II) and oxidant concentrations, pH, flow rate, number of cycles (h), and the type of geologic media used. Manganese oxide coating exceeded 1700 mg kg for Ottawa sand and 130 mg kg for aquifer sand. The Pb adsorption exceeded 2200 mg kg for the Ottawa sand and 300 mg kg for the aquifer sand. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

A novel biodegradable β-cyclodextrin-based hydrogel for the removal of heavy metal ions.

PubMed

Huang, Zhanhua; Wu, Qinglin; Liu, Shouxin; Liu, Tian; Zhang, Bin

2013-09-12

A novel biodegradable β-cyclodextrin-based gel (CAM) was prepared and applied to the removal of Cd(2+), Pb(2+) and Cu(2+) ions from aqueous solutions. CAM hydrogel has a typical three-dimensional network structure, and showed excellent capability for the removal of heavy metal ions. The effect of different experimental parameters, such as initial pH, adsorbent dosage and initial metal ion concentration, were investigated. The adsorption isotherm data fitted well to the Freundlich model. The adsorption capacity was in the order Pb(2+)>Cu(2+)>Cd(2+) under the same experimental conditions. The maximum adsorption capacities for the metal ions in terms of mg/g of dry gel were 210.6 for Pb(2+), 116.41 for Cu(2+), and 98.88 for Cd(2+). The biodegradation efficiency of the resin reached 79.4% for Gloeophyllum trabeum. The high adsorption capacity and kinetics results indicate that CAM can be used as an alternative adsorbent to remove heavy metals from aqueous solution. Published by Elsevier Ltd.

Potential use of algae for heavy metal bioremediation, a critical review.

PubMed

Zeraatkar, Amin Keyvan; Ahmadzadeh, Hossein; Talebi, Ahmad Farhad; Moheimani, Navid R; McHenry, Mark P

2016-10-01

Algae have several industrial applications that can lower the cost of biofuel co-production. Among these co-production applications, environmental and wastewater bioremediation are increasingly important. Heavy metal pollution and its implications for public health and the environment have led to increased interest in developing environmental biotechnology approaches. We review the potential for algal biosorption and/or neutralization of the toxic effects of heavy metal ions, primarily focusing on their cellular structure, pretreatment, modification, as well as potential application of genetic engineering in biosorption performance. We evaluate pretreatment, immobilization, and factors affecting biosorption capacity, such as initial metal ion concentration, biomass concentration, initial pH, time, temperature, and interference of multi metal ions and introduce molecular tools to develop engineered algal strains with higher biosorption capacity and selectivity. We conclude that consideration of these parameters can lead to the development of low-cost micro and macroalgae cultivation with high bioremediation potential. Copyright © 2016 Elsevier Ltd. All rights reserved.

The potential of melt-mixed polypropylene-zeolite blends in the removal of heavy metals from aqueous media

NASA Astrophysics Data System (ADS)

Motsa, Machawe M.; Thwala, Justice M.; Msagati, Titus A. M.; Mamba, Bhekie B.

The continued deterioration of the water quality in natural water sources such as rivers and lakes has led to tensions amongst relevant stakeholders to such an extent that cooperative water resource management is being regarded as an ideal solution to culminate conflicts and maximise the benefits. The desire to develop technologies that combine the three most important aspects of integrated water resource management (namely social, economic and environmental) has been encouraged by relevant authorities. This paper therefore reports the application of clinoptilolite-polypropylene (CLI-PP) blends/composites for the removal of lead from aqueous media. Just like many other heavy metals, lead poses a threat to water and soil quality as well as to plant and animal health. The findings on the adsorption behaviour of clinoptilolite-polypropylene composites with respect to Pb 2+ are also reported here, with the aim of extending its application to wastewater and environmental water purification. The batch equilibrium adsorption method was employed and the influence of contact time, pH, initial metal-ion concentration, temperature and pretreatment was determined. The optimum pH was found to be between pH 6 and pH 8 while the maximum sorption of lead at optimal pH was 95%. No big difference was observed between the adsorption behaviour of composites functionalised with 20% and 30% clinoptilolite, respectively. The pretreatment with HCl and NaCl made a slight difference to the adsorption capacity of composites.

Surface Charge Development on Transition Metal Sulfides: An Electrokinetic Study

NASA Astrophysics Data System (ADS)

Bebie, Joakim; Schoonen, Martin A. A.; Fuhrmann, Mark; Strongin, Daniel R.

1998-02-01

The isoelectric points, pH i.e.p., of ZnS, PbS, CuFeS 2, FeS, FeS 2, NiS 2, CoS 2, and MnS 2 in NaCl supported electrolyte solutions are estimated to be between pH 3.3 and 0.6, with most of the isoelectric points below pH 2. The first electrokinetic measurements on NiS 2, CoS 2, and MnS 2 are reported here. Below pH i.e.p. the metal-sulfide surfaces are positively charged, above pH i.e.p. the surfaces are negatively charged. The addition of Me 2+ ions shifts the pH i.e.p. and changes the pH dependence considerably. The isoelectric points of the measured transition metal sulfides in the absence of metal ions or dissolved sulfide (H 2S or HS -) are in agreement with those found in earlier studies. The pH range of observed isoelectric points for metal sulfides (0.6-3.3) is compared to the considerably wider pH i.e.p. range (2-12) found for oxides. The correlation between pH i.e.p. and the electronegativities of the metal sulfides suggests that all metal sulfides will have an isoelectric point between pH 0.6 and 3.3. Compared to metal oxides, sulfides exhibit an isoelectric point that is largely independent of the nature of the metal cation in the solid.

Remediation of AMD using natural and waste material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basir, Nur Athirah Mohamad; Yaacob, Wan Zuhairi Wan

2014-09-03

Acid Mine Drainage (AMD) is highly acidic, sulphate rich and frequently carries a high transition metal and heavy metal burden. These AMD's eventually migrate into streams and rivers and impact negatively on the quality of these water bodies. So it is dire necessary to treat this AMD. Various materials such as ladle furnace slag (LFS), bentonite, zeolite, active carbon and kaolinite are currently available to remove heavy metals from contaminated water. All these materials are capable to rise up the pH value and adsorb heavy metals. The process is divided into two stages; screening test and tank experiment. Screening testmore » is conduct by using Batch Equilibrium Test (BET), X-Ray Fluorescene (XRF) identification also Scanning Electron Microscopic (SEM) characteristic. The results showed that all the concentration of heavy metal are decreasing extremely and pH value rise up except for kaolinite. From screening test only ladle furnace slag, bentonite, zeolite and active carbon are chosen for the tank experiment. Tank experiment design with 18cm (H) X 15cm (L) X 15cm (H) was made by silica glass. All these treatment materials were stirred in the tank for 30 days. Initial pH for all tanks is 2.4 and after 30 days is changing into 6.11, 3.91, 2.98 and 2.71 for LFS, bentonite, active carbon as well as zeolite respectively. LFS is the best material for absorption of Zn, Mn and Cu in the synthetic solution. Meanwhile, bentonite is the best absorbent for Ni, Fe and Cd. The conclusion shows that LFS might have big potentials to control AMD pollution base on neutralize pH resulting in a great improvement in the quality of the water.« less

Remediation of AMD using natural and waste material

NASA Astrophysics Data System (ADS)

Basir, Nur Athirah Mohamad; Yaacob, Wan Zuhairi Wan

2014-09-01

Acid Mine Drainage (AMD) is highly acidic, sulphate rich and frequently carries a high transition metal and heavy metal burden. These AMD's eventually migrate into streams and rivers and impact negatively on the quality of these water bodies. So it is dire necessary to treat this AMD. Various materials such as ladle furnace slag (LFS), bentonite, zeolite, active carbon and kaolinite are currently available to remove heavy metals from contaminated water. All these materials are capable to rise up the pH value and adsorb heavy metals. The process is divided into two stages; screening test and tank experiment. Screening test is conduct by using Batch Equilibrium Test (BET), X-Ray Fluorescene (XRF) identification also Scanning Electron Microscopic (SEM) characteristic. The results showed that all the concentration of heavy metal are decreasing extremely and pH value rise up except for kaolinite. From screening test only ladle furnace slag, bentonite, zeolite and active carbon are chosen for the tank experiment. Tank experiment design with 18cm (H) X 15cm (L) X 15cm (H) was made by silica glass. All these treatment materials were stirred in the tank for 30 days. Initial pH for all tanks is 2.4 and after 30 days is changing into 6.11, 3.91, 2.98 and 2.71 for LFS, bentonite, active carbon as well as zeolite respectively. LFS is the best material for absorption of Zn, Mn and Cu in the synthetic solution. Meanwhile, bentonite is the best absorbent for Ni, Fe and Cd. The conclusion shows that LFS might have big potentials to control AMD pollution base on neutralize pH resulting in a great improvement in the quality of the water.

Titania-Coated Silica Alone and Modified by Sodium Alginate as Sorbents for Heavy Metal Ions

NASA Astrophysics Data System (ADS)

Kołodyńska, D.; Gęca, M.; Skwarek, E.; Goncharuk, O.

2018-04-01

The novel organic-inorganic biohybrid composite adsorbent was synthesized based on nanosized silica-titania modified with alginate within the development of effective adsorbent for heavy metal ions. Effects of metal species Cu(II), Zn(II), Cd(II), and Pb(II); concentrations; pH; temperature; and adsorption onto titania-coated silica (ST20) initial or modified by sodium alginate (ST20-ALG) were studied. The equilibrium and kinetic data of metal ions adsorption were analyzed using Langmuir and Freundlich adsorption models and kinetic models: pseudo first order, pseudo second order, intraparticle kinetic model, and Elovich. The maximum sorption capacities observed were higher for the ST20-ALG composite compared to the initial ST20 oxide for all studied metal ions, namely their values for ST20-ALG were 22.44 mg g- 1 for Cu(II) adsorption, 19.95 mg g- 1 for Zn(II), 18.85 mg g- 1 for Cd(II), and 32.49 mg g- 1 for Pb(II). Structure and properties of initial silica-titania ST20 and modified by sodium alginate ST20-ALG adsorbents were analyzed using nitrogen adsorption/desorption isotherms, ATR-FTIR, SEM-EDS, and pHpzc techniques.

PH DEPENDENT TOXICITY OF FIVE METALS TO THREE MARINE ORGANISMS

EPA Science Inventory

The pH of natural marine systems is relatively stable; this may explain why metal toxicity changes with pH have not been well documented. However, changes in metal toxicity with pH in marine waters are of concern in toxicity testing. During porewater toxicity testing pH can chang...

Recycling 100Mo for direct production of 99mTc on medical cyclotrons

NASA Astrophysics Data System (ADS)

Kumlin, Joel O.; Zeisler, Stefan K.; Hanemaayer, Victoire; Schaffer, Paul

2018-05-01

A scalable recycling technique for the recovery of 100Mo from previously irradiated and chemically processed targets is described. A combined process for both Cu and Ta supported targets and the respective `waste' solutions has been developed. This process involves selectively dissolving Cu target backings from undissolved portions of 100Mo pellets; precipitating Cu(OH)2 at pH 9; electrochemical removal of Cu traces; precipitating (NH4)2MoO4 at pH 2.5-3; thermally decomposing (NH4)2MoO4; and H2 reduction of MoO3 to Mo metal. Radionuclidic decontamination by a factor of 100 is observed, while overall 100Mo recovery from initial target plating to recycled Mo metal of 96% is achieved.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

PubMed

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

2017-09-28

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

Nickel adsorption by magnetic alginate microcapsules containing an extractant.

PubMed

Ngomsik, Audrey-Flore; Bee, Agnès; Siaugue, Jean-Michel; Cabuil, Valérie; Cote, Gérard

2006-05-01

The adsorption of heavy metals on biomaterials was investigated by studying the potential of alginate microcapsules containing an extractant (Cyanex 272) and magnetic nanoparticles (gamma-Fe2O3) for the adsorption of nickel (II) from aqueous solutions. A two-stage kinetics behaviour was observed with 70% of the maximum sorption capacity achieved within 8 h. An increase in nickel removal with increase in pH occurred, the maximum uptake capacity being around 0.42 mmol g-1 at pH 8. The adsorption isotherm (pH about 5.3) was obtained in a wide range of initial nickel concentrations; the experimental data were fitted by a Langmuir model and the qmax value was estimated to be 0.52 mmol g-1. Moreover, including magnetic particles in the microcapsules allowed easy isolation of the beads from the aqueous solutions after the sorption process. Magnetic microcapsules are then suitable for the development of efficient biosorbents for removal and recovery of heavy metals from wastewater using magnetic separation.

Preparation and adsorption behavior of aminated electrospun polyacrylonitrile nanofiber mats for heavy metal ion removal.

PubMed

Kampalanonwat, Pimolpun; Supaphol, Pitt

2010-12-01

Polyacrylonitrile (PAN) nanofiber mats were prepared by electrospinning and they were further modified to contain amidino diethylenediamine chelating groups on their surface via heterogeneous reaction with diethylenetriamine (DETA). The obtained aminated PAN (APAN) nanofiber mats were evaluated for their chelating property with four types of metal ions, namely Cu(II), Ag(I), Fe(II), and Pb(II) ions. The amounts of the metal ions adsorbed onto the APAN nanofiber mats were influenced by the initial pH and the initial concentration of the metal ion solutions. Increasing the contact time also resulted in a monotonous increase in the adsorbed amounts of the metal ions, which finally reached equilibria at about 10 h for Cu(II) ions and about 5 h for Ag(I), Fe(II), and Pb(II) ions. The maximal adsorption capacities of the metal ions on the APAN nanofiber mats, as calculated from the Langmuir model, were 150.6, 155.5, 116.5, and 60.6 mg g(-1), respectively. Lastly, the spent APAN nanofiber mats could be facilely regenerated with a hydrochloric acid (HCl) aqueous solution.

Influence of voltage input to heavy metal removal from electroplating wastewater using electrocoagulation process

NASA Astrophysics Data System (ADS)

Wulan, D. R.; Cahyaningsih, S.; Djaenudin

2017-03-01

In medium capacity, electroplating industry usually treats wastewater until 5 m3 per day. Heavy metal content becomes concern that should be reduced. Previous studies performed electrocoagulation method on laboratory scale, either batch or continuous. This study was aimed to compare the influence of voltage input variation into heavy metal removal in electroplating wastewater treatment using electrocoagulation process on laboratory-scale in order to determine the optimum condition for scaling up the reactor into pilot-scale. The laboratory study was performed in 1.5 L glass reactor in batch system using wastewater from electroplating industry, the voltage input varied at 20, 30 and 40 volt. The electrode consisted of aluminium 32 cm2 as sacrifice anode and copper 32 cm2 as cathode. During 120 min electrocoagulation process, the pH value was measured using pH meter, whereas the heavy metal of chromium, copper, iron, and zinc concentration were analysed using Atomic Absorption Spectrophotometer (AAS). Result showed that removal of heavy metals from wastewater increased due to the increasing of voltage input. Different initial concentration of heavy metals on wastewater, resulted the different detention time. At pilot-scale reactor with 30 V voltage input, chromium, iron, and zinc reached removal efficiency until 89-98%, when copper reached 79% efficiency. At 40V, removal efficiencies increased on same detention time, i.e. chromium, iron, and zinc reached 89-99%, whereas copper reached 85%. These removal efficiencies have complied the government standard except for copper that had higher initial concentration in wastewater. Kinetic rate also calculated in this study as the basic factor for scaling up the process.

Biosorption of Copper (II) from Aqueous Solution Using Non-Living Mesorhizobium amorphae Strain CCNWGS0123

PubMed Central

Mohamad, Osama Abdalla; Hao, Xiuli; Xie, Pin; Hatab, Shaimaa; Lin, Yanbing; Wei, Gehong

2012-01-01

The mining industry generates huge amounts of wastewater, containing toxic heavy metals. Treatment to remove heavy metals is necessary and recent work has been focused on finding more environmentally friendly materials for removing heavy metals from wastewater. Biosorption can be an effective process for heavy metal removal from aqueous solutions. Our objectives were to investigate the removal of copper (II) from aqueous solutions using dead cells of Mesorhizobium amorphae CCNWGS0123 under differing levels of pH, agitation speed, temperature, initial copper concentration, biosorbent dose and contact time using flame atomic absorption spectroscopy for metal estimation. The maximum copper removal rate was achieved at pH 5.0, agitation speed 150×g, temperature 28°C and initial Cu (II) concentration of 100 mg L−1. Maximum biosorption capacity was at 0.5 g L−1 and equilibrium was attained within 30 min. Langmuir and Freundlich isotherms showed correlation coefficients of 0.958 and 0.934, respectively. Fourier transform-infrared spectroscopy (FT-IR) analysis indicated that many functional groups, such as O-H, N-H, C-H, C=O, -NH, -CN, C-N, C-O, amide -I, -II, -III and unsaturated alkenes, alkyls and aromatic groups on the cell surface were involved in the interaction between CCNWGS0123 and Cu. Scanning electron microscope and energy dispersive X-ray scanning results showed deformation, aggregation, and cell-surface damage due to the precipitation of copper on the cell surface. Dead cells of CCNWGS0123 showed potential as an efficient biosorbent for the removal of Cu2+ from aqueous solutions. PMID:22353770

Factors Affecting Oxidation of Thiosalts by Thiobacilli

PubMed Central

Silver, M.; Dinardo, O.

1981-01-01

The effects of temperature, initial pH, and the concentrations of ammonium, phosphate, and heavy metals on the oxidation of thiosalts by an authentic strain of Thiobacillus thiooxidans (ATCC 8085) and by a mixed culture isolated from a base metal-processing mill effluent pond were studied. The optimum temperature was 30°C and the optimum initial pH was 3.75 for both cultures using thiosulfate and for the mixed culture using tetrathionate. T. thiooxidans ATCC 8085 did not oxidize tetrathionate. For a thiosalt concentration of 2,000 ppm (2,000 mg/liter), maximal rates of destruction occurred at concentrations of ammonium ion above 2 mg/liter and in the presence of 1 mg of phosphate per liter. Under optimal conditions, the rate of thiosulfate oxidation by the pure culture was 55 ± 3 mg/liter per h; the mixed culture oxidized thiosulfate at the rate of 40 ± 1 mg/liter per h and tetrathionate at the rate of 50 ± 2 mg/liter per h. Metal ions caused normal inhibition kinetics in the oxidation of thiosulfate by T. thiooxidans ATCC 8085. Ki values were calculated for cadmium (16 mg/liter), copper (0.46 mg/liter), lead (2 mg/liter), silver (3.1 mg/liter), and zinc (33 mg/liter). Only a slight additive effect was apparent in the presence of all of these metal ions. The mixed culture of thiosalt-oxidizing bacteria was less sensitive to heavy metal inhibition; the order of inhibition of thiosulfate oxidation was Cd < Zn < Pb < Ag < Cu, and that of tetrathionate oxidation was Zn < Cd < Pb < Ag < Cu. PMID:16345785

Cr(VI) removal from aqueous solution by thermophilic denitrifying bacterium Chelatococcus daeguensis TAD1 in the presence of single and multiple heavy metals.

PubMed

Li, Han; Huang, Shaobin; Zhang, Yongqing

2016-09-01

Cr(VI) pollution is increasing continuously as a result of ongoing industrialization. In this study, we investigated the thermophilic denitrifying bacterium Chelatococcus daeguensis TAD1, isolated from the biofilm of a biotrickling filter used in nitrogen oxides (NOX) removal, with respect to its ability to remove Cr(VI) from an aqueous solution. TAD1 was capable of reducing Cr(VI) from an initial concentration of 10 mg/L to non-detectable levels over a pH range of 7-9 and at a temperature range of 30-50°C. TAD1 simultaneously removed both Cr(VI) and NO3 (-)-N at 50°C, when the pH was 7 and the initial Cr(VI) concentration was 15 mg/L. The reduction of Cr(VI) to Cr(III) correlated with the growth metabolic activity of TAD1. The presence of other heavy metals (Cu, Zn, and Ni) inhibited the ability of TAD1 to remove Cr(VI). The metals each individually inhibited Cr(VI) removal, and the extent of inhibition increased in a cooperative manner in the presence of a combination of the metals. The addition of biodegradable cellulose acetate microspheres (an adsorption material) weakened the toxicity of the heavy metals; in their presence, the Cr(VI) removal efficiency returned to a high level. The feasibility and applicability of simultaneous nitrate removal and Cr(VI) reduction by strain TAD1 is promising, and may be an effective biological method for the clean-up of wastewater.

Effect of nitrate and ammonium fertilization on Zn, Pb, and Cd phytostabilization by Populus euramericana Dorskamp in contaminated technosol.

PubMed

Qasim, Bashar; Motelica-Heino, Mikael; Bourgerie, Sylvain; Gauthier, Arnaud; Morabito, Domenico

2015-12-01

This study aimed at assessing the effect of nitrogen addition under two forms, nitrate and ammonium, on the stabilization of Zn, Pb, and Cd by Populus euramericana Dorskamp grown in contaminated soils for 35 days under controlled conditions. Temporal changes in the soil pore water (SPW) were monitored for pH, dissolved organic carbon (DOC), and total dissolved concentrations of metals in the soils rhizosphere. Rhizospheric SPW pH decreased gradually with NH4(+) addition and increased with NO3(-) addition up to one unit, while it slightly decreased initially then increased for the untreated control soil DOC increased with time up to six times, the highest increase occurring with NH4(+) fertilization. An increase in the metal concentrations in the rhizospheric SPW was observed for NH4(+) addition associated with the lowest rhizospheric SPW pH, whereas the opposite was observed for the control soil and NO3(-) fertilization. Fertilization did not affect plant shoots or roots biomass development compared to the untreated control (without N addition). Metals were mostly accumulated in the rhizosphere and N fertilization increased the accumulation for Zn and Pb while Cd accumulation was enhanced for NH4(+) addition. Collectively, our results suggest metal stabilization by P. euramericana Dorskamp rhizosphere with nitrogen fertilization and are potential for phytostabilization of contaminated technosol.

Colloid mobilization and heavy metal transport in the sampling of soil solution from Duckum soil in South Korea.

PubMed

Lee, Seyong; Ko, Il-Won; Yoon, In-Ho; Kim, Dong-Wook; Kim, Kyoung-Woong

2018-03-24

Colloid mobilization is a significant process governing colloid-associated transport of heavy metals in subsurface environments. It has been studied for the last three decades to understand this process. However, colloid mobilization and heavy metal transport in soil solutions have rarely been studied using soils in South Korea. We investigated the colloid mobilization in a variety of flow rates during sampling soil solutions in sand columns. The colloid concentrations were increased at low flow rates and in saturated regimes. Colloid concentrations increased 1000-fold higher at pH 9.2 than at pH 7.3 in the absence of 10 mM NaCl solution. In addition, those were fourfold higher in the absence than in the presence of the NaCl solution at pH 9.2. It was suggested that the mobility of colloids should be enhanced in porous media under the basic conditions and the low ionic strength. In real field soils, the concentrations of As, Cr, and Pb in soil solutions increased with the increase in colloid concentrations at initial momentarily changed soil water pressure, whereas the concentrations of Cd, Cu, Fe, Ni, Al, and Co lagged behind the colloid release. Therefore, physicochemical changes and heavy metal characteristics have important implications for colloid-facilitated transport during sampling soil solutions.

Application of mucilage from Dicerocaryum eriocarpum plant as biosorption medium in the removal of selected heavy metal ions.

PubMed

Jones, Bassey O; John, Odiyo O; Luke, Chimuka; Ochieng, Aoyi; Bassey, Bridget J

2016-07-15

The ability of mucilage from Dicerocaryum eriocarpum (DE) plant to act as biosorption medium in the removal of metals ions from aqueous solution was investigated. Functional groups present in the mucilage were identified using Fourier transform infrared spectroscopy (FTIR). Mucilage was modified with sodium and potassium chlorides. This was aimed at assessing the biosorption efficiency of modified mucilage: potassium mucilage (PCE) and sodium mucilage (SCE) and comparing it with non-modified deionised water mucilage (DCE) in the uptake of metal ions. FTIR results showed that the functional groups providing the active sites in PCE and SCE and DCE include: carboxyl, hydroxyl and carbonyl groups. The chloride used in the modification of the mucilage did not introduce new functional groups but increased the intensity of the already existing functional groups in the mucilage. Results from biosorption experiment showed that DE mucilage displays good binding affinity with metals ions [Zn(II), Cd(II) Ni(II), Cr(III) and Fe(II)] in the aqueous solution. Increase in the aqueous solution pH, metal ions initial concentration and mucilage concentration increased the biosorption efficiency of DE mucilage. The maximum contact time varied with each species of metal ions. Optimum pH for [Zn(II), Cd(II) Ni(II) and Fe(II)] occurred at pH 4 and pH 6 for Cr(III). Kinetic models result fitted well to pseudo-second-order with a coefficient values of R(2) = 1 for Cd(II), Ni(II), Cr(III), Fe(II) and R(2) = 0.9974 for Zn(II). Biosorption isotherms conforms best with Freundlich model for all the metal ions with correlation factors of 0.9994, 0.9987, 0.9554, 0.9621 and 0.937 for Zn(II), Ni(II), Fe(II), Cr(III) and Cd(II), respectively. Biosorption capacity of DE mucilage was 0.010, 2.387, 4.902, 0688 and 0.125 for Zn(II), Cr(III), Fe(II), Cd(II) and Ni(II) respectively. The modified mucilage was found to be highly efficient in the removal of metal ions than the unmodified mucilage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Bioleaching in batch tests for improving sludge dewaterability and metal removal using Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans after cold acclimation.

PubMed

Zhou, Qingyang; Gao, Jingqing; Li, Yonghong; Zhu, Songfeng; He, Lulu; Nie, Wei; Zhang, Ruiqin

2017-09-01

Bioleaching is a promising technology for removal of metals from sludge and improvement of its dewaterability. Most of the previous studies of bioleaching were focused on removal of metals; bioleaching in cold environments has not been studied extensively. In this study, Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans were acclimated at 15 °C and co-inoculated to explore the optimal conditions for improvement of sludge dewaterability and removal of metals by the sequencing batch reactors. The data show after 6 days of bioleaching at 15 °C, 89.6% of Zn, 72.8% of Cu and 39.4% of Pb were removed and the specific resistance to filtration (SRF) was reduced to ∼12%. In addition, the best conditions for bioleaching are an initial pH of 6, a 15% (v/v) inoculum concentration, and A. thiooxidans and A. ferrooxidans mixed in a ratio of 4:1. We found that bioleaching of heavy metals is closely related to final pH, while the sludge SRF is dominated by other factors. Bioleaching can be completed in 6 days, and the sludge dewaterability and removal of metals at 15 °C meet the requirements of most sewage treatment plants.

Biosorption of Cd(II) and Cs(I) from aqueous solution by live and dead cells of Saccharomyces carlsbergensis PTCC 5051.

PubMed

Sayyadi, Shayan; Ahmady-Asbchin, Salman; Kamali, Kasra

2018-02-01

The biosorption characteristics of Cd(II) and Cs(I) using live and dead cells of Saccharomyces carlsbergensis PTCC 5051 as biosorbents have been investigated in the present research. The influence of different experimental parameters such as initial pH (pHi), shaking rate, sorption time and initial metal concentration was evaluated. The optimum pH was obtained as 4 for Cd(II) and 7 for Cs(I). The experimental adsorption data were fitted to the Langmuir linear equation adsorption model. The highest metal uptake values of 0.593 and 0.473 mmol g -1 were calculated for Cd(II) and Cs(I), respectively. The results of Fourier transform infrared analysis suggested the involvement of amine, carboxyl and hydroxyl groups during the biosorption process and also indicated that more functional groups were involved in the biosorption process of live adsorbents, compared with those linked to dead biomass. The results showed that the biomass of S. carlsbergensis PTCC 5051 is a suitable biosorbent for the removal of Cd(II) and Cs(I) from the aqueous solutions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Degtyarenko, N. N.; Mazur, E. A., E-mail: eugen-mazur@mail.ru

The structural, electronic, phonon, and other characteristics of the normal phases of phosphorus hydrides with stoichiometry PH{sub k} are analyzed. The properties of the initial substance, namely, diphosphine are calculated. In contrast to phosphorus hydrides with stoichiometry PH{sub 3}, a quasi-two-dimensional phosphorus-stabilized lattice of metallic hydrogen can be formed in this substance during hydrostatic compression at a high pressure. The formed structure with H–P–H elements is shown to be locally stable in phonon spectrum, i.e., to be metastable. The properties of diphosphine are compared with the properties of similar structures of sulfur hydrides.

Biosorption studies on copper (II) and cadmium (II) using pretreated rice straw and rice husk.

PubMed

Li, W C; Law, F Y; Chan, Y H M

2017-04-01

This study investigated the adsorption and removal behaviour of copper (Cu) (II) and cadmium (Cd) (II) ions using rice husk and rice straw in aqueous solutions. Different parameters were used to investigate their adsorption performance in saline conditions and the optimal level of biosorption at different pH levels. The main parameters were pH (3, 6 and 9), initial concentration level of heavy metals (Cu (II) 5, 10, 20, 40 and 60 mg/L and Cd (II) 0.5, 1, 2, 4 and 8 mg/L, respectively), salinity (0, 50 and 100 mM NaCl) and contact time (ranging from 3 to 60 min). Langmuir and Freundlich isotherm models were applied to analyse the removal efficiency and sorption capacity of the pretreated rice husk and rice straw. The removal efficiency and adsorption capacity generally increased with the pH and reached a plateau in alkaline conditions. The percentage removal of Cu (II) by rice husk reached 97 % at pH 9 and 95 % by rice straw at pH 6. Biosorption performance increased in the absence of NaCl. Kinetic studies for both metals revealed that the biosorption of Cu (II) and Cd (II) onto rice straw and husk was pseudo-second order.

The effect of oxide film properties on the corrosion behavior of SiC/Al metal-matrix composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Golledge, S.L.

1991-01-01

Oxide growth on pure aluminum, aluminum alloy 6061, and the aluminum-based metal matrix composite SiC/AA6061 was studied, and the properties of the oxides related to the pit-initiation behavior of the materials. The objectives of the work were to identify the effect of alloying elements and SiC reinforcement on the oxide film, and to better understand how the oxide properties control pit initiation behavior. To this end, electrochemical and optical studies of the materials were carried out in a buffered sodium/boric acid solution at pH values of 8.4 and 7.2. The alloy and metal-matrix composite showed a slightly lesser tendency tomore » pit than pure aluminum, as measured by the pitting potential. The oxide on the composite was less resistant to pit initiation, and was found to exhibit slower repassivation rates than the other materials. The repassivation behavior and resistance to pit initiation were quite similar in the case of the alloy and the pure aluminum. Induction times for pit initiation were consistent with the predictions of Heusler's model for the breakdown of passivity.« less

Bioleaching combined brine leaching of heavy metals from lead-zinc mine tailings: Transformations during the leaching process.

PubMed

Ye, Maoyou; Yan, Pingfang; Sun, Shuiyu; Han, Dajian; Xiao, Xiao; Zheng, Li; Huang, Shaosong; Chen, Yun; Zhuang, Shengwei

2017-02-01

During the process of bioleaching, lead (Pb) recovery is low. This low recovery is caused by a problem with the bioleaching technique. This research investigated the bioleaching combination of bioleaching with brine leaching to remove heavy metals from lead-zinc mine tailings. The impact of different parameters were studied, including the effects of initial pH (1.5-3.0) and solid concentration (5-20%) for bioleaching, and the effects of sodium chloride (NaCl) concentration (10-200 g/L) and temperature (25 and 50 °C) for brine leaching. Complementary characterization experiments (Sequential extraction, X-ray diffractometer (XRD), scanning electronic microscope (SEM)) were also conducted to explore the transformation of tailings during the leaching process. The results showed that bioleaching efficiency was significantly influenced by initial pH and solid concentration. Approximately 85.45% of iron (Fe), 4.12% of Pb, and 97.85% of zinc (Zn) were recovered through bioleaching in optimum conditions. Increasing the brine concentration and temperature promoted lead recovery. Lead was recovered from the bioleaching residues at a rate of 94.70% at 25 °C and at a rate of 99.46% at 50 °C when the NaCl concentration was 150 g/L. The study showed that bioleaching significantly changed the speciation of heavy metals and the formation and surface morphology of tailings. The metals were mainly bound in stable fractions after bioleaching. Copyright © 2016 Elsevier Ltd. All rights reserved.

Leaching of DOC, DN, and inorganic constituents from scrap tires.

PubMed

Selbes, Meric; Yilmaz, Ozge; Khan, Abdul A; Karanfil, Tanju

2015-11-01

One concern for recycle and reuse of scrap tires is the leaching of tire constituents (organic and inorganic) with time, and their subsequent potential harmful impacts in environment. The main objective of this study was to examine the leaching of dissolved organic carbon (DOC), dissolved nitrogen (DN), and selected inorganic constituents from scrap tires. Different sizes of tire chips and crumb rubber were exposed to leaching solutions with pH's ranging from 3.0 to 10.0 for 28days. The leaching of DOC and DN were found to be higher for smaller size tire chips; however, the leaching of inorganic constituents was independent of the size. In general, basic pH conditions increased the leaching of DOC and DN, whereas acidic pH conditions led to elevated concentrations of metals. Leaching was minimal around the neutral pH values for all the monitored parameters. Analysis of the leaching rates showed that components associated with the rubbery portion of the tires (DOC, DN, zinc, calcium, magnesium, etc.) exhibited an initial rapid followed by a slow release. On the other hand, a constant rate of leaching was observed for iron and manganese, which are attributed to the metal wires present inside the tires. Although the total amounts that leached varied, the observed leaching rates were similar for all tire chip sizes and leaching solutions. Operation under neutral pH conditions, use of larger size tire chips, prewashing of tires, and removal of metal wires prior to application will reduce the impact of tire recycle and reuse. Copyright © 2015 Elsevier Ltd. All rights reserved.

Uptake of Cr3+ from aqueous solution by lignite-based humic acids.

PubMed

Arslan, G; Pehlivan, E

2008-11-01

Humic acid (HA) produced from brown coal, a relatively abundant and inexpensive material is currently being investigated as an adsorbent to remove toxic metals from aqueous solution. The influence of five parameters (contact time, solution pH, initial metal concentration, temperature and amount of adsorbent) on the removal at 20+/-1 degrees C was studied. HAs were prepared from lignites by using alkaline extraction, sedimentation and acidic precipitation. Adsorption equilibrium was achieved in about 60 min for Cr3+ ion. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The maximum adsorption capacity of 0.17 mmol for Ilgin (HA1), 0.29 mmol for Beysehir (HA2) and 0.18 mmol Ermenek (HA3) and 0.17 mmol of Cr3+/g for activated carbon (AC) was achieved, respectively at pH of 4.1. More than 84% of Cr3+ was removed by HA2, 54% by HA3 and 51% by HA1 and 50% by AC from aqueous solution. The adsorption was strongly dependent on pH but independent of ionic strength and metal ions. The adsorption of Cr3+ was higher between pH 4.1 and 5.1 for all HAs and maximum sorption was observed at pH 4.1. The rise in temperature caused a slight decrease in the value of the equilibrium constant (Kc) for the sorption of Cr3+ ion. Complex mechanisms including ion exchange, complexation and adsorption and size exclusion are possible for sorption of Cr3+ ion on HAs.

Enhanced chitosan beads-supported Fe(0)-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers.

PubMed

Liu, Tingyi; Yang, Xi; Wang, Zhong-Liang; Yan, Xiaoxing

2013-11-01

The removal of heavy metals from electroplating wastewater is a matter of paramount importance due to their high toxicity causing major environmental pollution problems. Nanoscale zero-valent iron (NZVI) became more effective to remove heavy metals from electroplating wastewater when enhanced chitosan (CS) beads were introduced as a support material in permeable reactive barriers (PRBs). The removal rate of Cr (VI) decreased with an increase of pH and initial Cr (VI) concentration. However, the removal rates of Cu (II), Cd (II) and Pb (II) increased with an increase of pH while decreased with an increase of their initial concentrations. The initial concentrations of heavy metals showed an effect on their removal sequence. Scanning electron microscope images showed that CS-NZVI beads enhanced by ethylene glycol diglycidyl ether (EGDE) had a loose and porous surface with a nucleus-shell structure. The pore size of the nucleus ranged from 19.2 to 138.6 μm with an average aperture size of around 58.6 μm. The shell showed a tube structure and electroplating wastewaters may reach NZVI through these tubes. X-ray photoelectron spectroscope (XPS) demonstrated that the reduction of Cr (VI) to Cr (III) was complete in less than 2 h. Cu (II) and Pb (II) were removed via predominant reduction and auxiliary adsorption. However, main adsorption and auxiliary reduction worked for the removal of Cd (II). The removal rate of total Cr, Cu (II), Cd (II) and Pb (II) from actual electroplating wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively. The findings revealed that EGDE-CS-NZVI-beads PRBs had the capacity to remediate actual electroplating wastewater and may become an effective and promising technology for in situ remediation of heavy metals. Copyright © 2013 Elsevier Ltd. All rights reserved.

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

Remediation of Hg(II) from solutions using Cajanus cajan husk as a new sorbent.

PubMed

Devani, Mallappa A; Munshi, Basudeb; Oubagaranadin, John U Kennedy; Lal, Bipin Bihari; Mandal, Sandip

2017-08-01

In this work, biosorption of mercury(II) from solutions by normal and chemically modified husk of Cajanus cajan has been explored under batch conditions. The thermogravimetric analysis of the normal biosorbent showed a surface water loss of 6.56%, 9.26% volatile matter, and 81.81% organic matter. The scanning electron microscope image indicates that the biosorbent exhibited irregular and porous structures. The Fourier transform infra-red spectrum confirmed the presence of functional groups which are responsible for biosorption of mercury (II) from solutions after activation. The influence of initial pH of solutions, initial metal concentrations, and temperature on mercury(II) uptake by the biosorbents was evaluated. The biosorption followed the Langmuir model. Maximum metal uptake was obtained as 68 and 82 mg/g for an initial mercury(II) concentration of 150 mg/L for normal and chemically activated biosorbents, respectively, at a most favorable solution pH of 5.5. The kinetics of sorption obeyed the pseudo-second-order model. An endothermic nature of the biosorption process was observed. A two-stage biosorber reduced the consumption of the biosorbents by 3.49% and 16.52% for 100 and 150 mg/L, respectively. The novelty of the work is C. cajan husk proves to be a potential biosorbent for mercury(II) from solutions.

Formation of metal-nicotianamine complexes as affected by pH, ligand exchange with citrate and metal exchange. A study by electrospray ionization time-of-flight mass spectrometry.

PubMed

Rellán-Alvarez, Rubén; Abadía, Javier; Alvarez-Fernández, Ana

2008-05-01

Nicotianamine (NA) is considered as a key element in plant metal homeostasis. This non-proteinogenic amino acid has an optimal structure for chelation of metal ions, with six functional groups that allow octahedral coordination. The ability to chelate metals by NA is largely dependent on the pK of the resulting complex and the pH of the solution, with most metals being chelated at neutral or basic pH values. In silico calculations using pKa and pK values have predicted the occurrence of metal-NA complexes in plant fluids, but the use of soft ionization techniques (e.g. electrospray), together with high-resolution mass spectrometers (e.g. time-of-flight mass detector), can offer direct and metal-specific information on the speciation of NA in solution. We have used direct infusion electrospray ionization mass spectrometry (time-of-flight) ESI-MS(TOF) to study the complexation of Mn, Fe(II), Fe(III), Ni, Cu by NA. The pH dependence of the metal-NA complexes in ESI-MS was compared to that predicted in silico. Possible exchange reactions that may occur between Fe-NA and other metal micronutrients as Zn and Cu, as well as between Fe-NA and citrate, another possible Fe ligand candidate in plants, were studied at pH 5.5 and 7.5, values typical of the plant xylem and phloem saps. Metal-NA complexes were generally observed in the ESI-MS experiments at a pH value approximately 1-2 units lower than that predicted in silico, and this difference could be only partially explained by the estimated error, approximately 0.3 pH units, associated with measuring pH in organic solvent-containing solutions. Iron-NA complexes are less likely to participate in ligand- and metal-exchange reactions at pH 7.5 than at pH 5.5. Results support that NA may be the ligand chelating Fe at pH values usually found in phloem sap, whereas in the xylem sap NA is not likely to be involved in Fe transport, conversely to what occurs with other metals such as Cu and Ni. Some considerations that need to be addressed when studying metal complexes in plant compartments by ESI-MS are also discussed.

Removal of copper(II) ions from aqueous solutions by Azolla rongpong: batch and continuous study.

PubMed

Nedumaran, B; Velan, M

2008-01-01

Batch and packed bed continuous biosorption studies were conducted to investigate the kinetics and isotherms of Cu(II) ions on the biomass of blue green alga Azolla rongpong. It is observed that the biosorption capacity of algae depends on initial pH and dosage. The biosorption capacity increases with increasing concentration and follows Freundlich isotherm model well with k and n values 0.06223 and 0.949 respectively. The optimum pH of 3.5 with an algae dosage of 1 g/L was observed. The results indicate that with the advantage of high metal biosorption capacity and recovery of Cu(II) ions, A. rongpong can be used as an efficient and economic biosorbent for the removal and recovery of toxic heavy metals from aqueous wastes even at higher concentration.

Ability of various plant species to prevent leakage of N, P, and metals from sewage sludge.

PubMed

Neuschütz, Clara; Greger, Maria

2010-01-01

The preventive effect of vegetation on nutrient and metal leakage from sewage sludge (SS) used in treatment of mine waste was investigated. In a 10-week greenhouse study, the release of ammonium, nitrate, phosphate, Cd, Cu, and Zn from SS was analyzed in the absence (control) and presence of basket willow, fireweed, reed Canary grass (RCG), and Scots pine. Plants significantly decreased the leakage by reducing the amount of leachate, and lowered the concentrations of phosphate (to 0.1 mg L(-1)), Cu (0.8 mg L(-1)), and Zn (2.2 mg L(-1)); and plants increased the pH in the leachate towards the end of the experiment. The most efficient plant was RCG that significantly decreased the total leakage of all pollutants. However, plants could not counteract high initial concentrations of ammonium and nitrate (< 400 mg L(-1) of both) and drop in pH (to 4.5), or increasing Cd release (< 9.7 microg L(-1)). RCG and fireweed used both ammonium and nitrate as nitrogen source and were more efficient in preventing nitrate leakage, compared with willow and pine that mainly used ammonium. This study indicates that introduction of RCG is a promising method for phytostabilization of SS, but that alkaline additives are needed to prevent an initial decrease in pH.

Equilibrium, Kinetic, and Thermodynamic Studies on the Adsorption of Cadmium from Aqueous Solution by Modified Biomass Ash

PubMed Central

Zheng, Xuebo; Cui, Hongbiao; Zhu, Zhenqiu; Liang, Jiani

2017-01-01

Natural biomass ash of agricultural residuals was collected from a power plant and modified with hexagonal mesoporous silica and functionalized with 3-aminopropyltriethoxysilane. The physicochemical and morphological properties of the biomass ash were analyzed by ICP-OES, SEM, TEM-EDS, FTIR, and BET analysis. The adsorption behavior of the modified product for Cd2+ in aqueous solution was studied as a function of pH, initial metal concentration, equilibrium time, and temperature. Results showed that the specific surface area of the modified product was 9 times that of the natural biomass ash. The modified biomass ash exhibited high affinity for Cd2+ and its adsorption capacity increased sharply with increasing pH from 4.0 to 6.0. The maximum adsorption capacity was 23.95 mg/g in a pH 5 solution with an initial metal concentration of 50 mg/L and a contact time of 90 min. The adsorption of Cd2+ onto the modified biomass ash was well fitted to the Langmuir model and it followed pseudo-second-order kinetics. Thermodynamic analysis results showed that the adsorption of Cd2+ was spontaneous and endothermic in nature. The results suggest that the modified biomass ash is promising for use as an inexpensive and effective adsorbent for Cd2+ removal from aqueous solution. PMID:28348509

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

PubMed Central

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

2017-01-01

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

Gas generation behavior of transuranic waste under disposal conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujisawa, Ryutaro; Kurashige, Tetsunari; Inagaki, Yusuke

1999-07-01

The generation of hydrogen-gas from metallic waste is an important issue for the safety analysis of geological disposal facilities for transuranic (TRU) radioactive waste in Japan. The objective of this study is to clarify the gas-generation behavior of stainless steel and carbon steel in non-oxidizing alkaline synthetic groundwater (pH 12.8 and 10.5) at 30 C simulating geological disposal environments. At pH 12.8, the observed gas-generation rate from stainless steel in the initial period of immersion was 1.0 x 10{sup 2} Nml/m{sup 2}/y and 1.0 x 10 Nml/m{sup 2}/y after 200 days (N represents the standard state of gas at 0more » C and 1 atm). At pH 10.5, gas generation was not observed for 60 days in the initial period. At 60 days, the gas-generation observed was 5.0 x 10 NMl/m{sup 2}/y. After 250 days, the gas-generation rate approaches zero. At pH 12.8, the observed gas generation rate of carbon steel in the initial period of immersion was 1.5 x 10{sup 2} Nml/m{sup 2}/y and the gas generation rate began to decrease after 200 days. After 300 days, it was 25 Nml/m{sup 2}/y. At pH 10.5, the gas generation rate in the initial period was 5.0 x 10{sup 2} Nml/m{sup 2}/y and was 1.0 x 10 Nml/m{sup 2}/y after 200 days.« less

Removal of mercury from its aqueous solution using charcoal-immobilized papain (CIP).

PubMed

Dutta, Susmita; Bhattacharyya, Aparupa; De, Parameswar; Ray, Parthasarathi; Basu, Srabanti

2009-12-30

In the present work mercury has been eradicated from its aqueous solution using papain, immobilized on activated charcoal by physical adsorption method. Operating parameters for adsorption of papain on activated charcoal like pH, amount of activated charcoal, initial concentration of papain in solution have been varied in a suitable manner for standardization of operating conditions for obtaining the best immobilized papain sample based on their specific enzymatic activity. The immobilized papain sample obtained at initial papain concentration 40.0 g/L, activated charcoal amount 0.5 g and pH 7 shows the best specific enzymatic activity. This sample has been designated as charcoal-immobilized papain (CIP) and used for further studies of mercury removal. Adsorption equilibrium data fit most satisfactorily with the Langmuir isotherm model for adsorption of papain on activated charcoal. Physicochemical characterization of CIP has been done. The removal of mercury from its simulated solution of mercuric chloride using CIP has been studied in a lab-scale batch contactor. The operating parameters viz., the initial concentration of mercury in solution, amount of CIP and pH have been varied in a prescribed manner. Maximum removal achieved in the batch study was about 99.4% at pH 7, when initial metal concentration and weight of CIP were 20.0mg/L and 0.03 g respectively. Finally, the study of desorption of mercury has been performed at different pH values for assessment of recovery process of mercury. The results thus obtained have been found to be satisfactory.

Preparation of transition metal composite graphite felt cathode for efficient heterogeneous electro-Fenton process.

PubMed

Liang, Liang; Yu, Fangke; An, Yiran; Liu, Mengmeng; Zhou, Minghua

2017-01-01

A composite graphite felt (GF) modified with transition metal was fabricated and used as cathode in heterogeneous electro-Fenton (EF) for methyl orange (MO) degradation. Characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), the morphology and surface physicochemical properties of the cathodes after modification were observed considerably changed. After loading metals, the current response became higher, the accumulation of H 2 O 2 and the degradation efficiency of MO were improved. Under the same conditions, GF-Co had the highest catalytic activity for electro-reduction of O 2 to H 2 O 2 and MO degradation. At pH 3, 99 % of MO degradation efficiency was obtained using GF-Co after 120 min treatment and even at initial pH 9, 82 % of that was obtained. TOC removal efficiency reached 93.8 % using GF-Co at pH 3 after 120 min treatment while that was 12.3 % using GF. After ten-time runs, the mineralization ratio of the GF-Co was still 89.5 %, suggesting that GF-Co was very promising for wastewater treatment. The addition of isopropanol proved that · OH played an important role in degradation of MO.

Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.

PubMed

Flynn, Elaine D; Catalano, Jeffrey G

2018-06-05

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

Disentangling the effects of low pH and metal mixture toxicity on macroinvertebrate diversity

USGS Publications Warehouse

Fornaroli, Riccardo; Ippolito, Alessio; Tolkkinen, Mari J.; Mykrä, Heikki; Muotka, Timo; Balistrieri, Laurie S.; Schmidt, Travis S.

2018-01-01

One of the primary goals of biological assessment of streams is to identify which of a suite of chemical stressors is limiting their ecological potential. Elevated metal concentrations in streams are often associated with low pH, yet the effects of these two potentially limiting factors of freshwater biodiversity are rarely considered to interact beyond the effects of pH on metal speciation. Using a dataset from two continents, a biogeochemical model of the toxicity of metal mixtures (Al, Cd, Cu, Pb, Zn) and quantile regression, we addressed the relative importance of both pH and metals as limiting factors for macroinvertebrate communities. Current environmental quality standards for metals proved to be protective of stream macroinvertebrate communities and were used as a starting point to assess metal mixture toxicity. A model of metal mixture toxicity accounting for metal interactions was a better predictor of macroinvertebrate responses than a model considering individual metal toxicity. We showed that the direct limiting effect of pH on richness was of the same magnitude as that of chronic metal toxicity, independent of its influence on the availability and toxicity of metals. By accounting for the direct effect of pH on macroinvertebrate communities, we were able to determine that acidic streams supported less diverse communities than neutral streams even when metals were below no-effect thresholds. Through a multivariate quantile model, we untangled the limiting effect of both pH and metals and predicted the maximum diversity that could be expected at other sites as a function of these variables. This model can be used to identify which of the two stressors is more limiting to the ecological potential of running waters.

Disentangling the effects of low pH and metal mixture toxicity on macroinvertebrate diversity.

PubMed

Fornaroli, Riccardo; Ippolito, Alessio; Tolkkinen, Mari J; Mykrä, Heikki; Muotka, Timo; Balistrieri, Laurie S; Schmidt, Travis S

2018-04-01

One of the primary goals of biological assessment of streams is to identify which of a suite of chemical stressors is limiting their ecological potential. Elevated metal concentrations in streams are often associated with low pH, yet the effects of these two potentially limiting factors of freshwater biodiversity are rarely considered to interact beyond the effects of pH on metal speciation. Using a dataset from two continents, a biogeochemical model of the toxicity of metal mixtures (Al, Cd, Cu, Pb, Zn) and quantile regression, we addressed the relative importance of both pH and metals as limiting factors for macroinvertebrate communities. Current environmental quality standards for metals proved to be protective of stream macroinvertebrate communities and were used as a starting point to assess metal mixture toxicity. A model of metal mixture toxicity accounting for metal interactions was a better predictor of macroinvertebrate responses than a model considering individual metal toxicity. We showed that the direct limiting effect of pH on richness was of the same magnitude as that of chronic metal toxicity, independent of its influence on the availability and toxicity of metals. By accounting for the direct effect of pH on macroinvertebrate communities, we were able to determine that acidic streams supported less diverse communities than neutral streams even when metals were below no-effect thresholds. Through a multivariate quantile model, we untangled the limiting effect of both pH and metals and predicted the maximum diversity that could be expected at other sites as a function of these variables. This model can be used to identify which of the two stressors is more limiting to the ecological potential of running waters. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metal ion removal from aqueous solution using physic seed hull.

PubMed

Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

2010-07-15

The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. 2010 Elsevier B.V. All rights reserved.

Porous silicon powder as an adsorbent of heavy metal (nickel)

NASA Astrophysics Data System (ADS)

Nabil, Marwa; Motaweh, Hussien A.

2018-04-01

New and inexpensive nanoporous silicon (NPS) powder was prepared by alkali chemical etching using sonication technique and was subsequently investigated as an adsorbent in batch systems for the adsorption Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the NPS powder were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and contact time. The results indicated that the maximum adsorption capacity and the maximum removal percent of Ni(II) reached 2665.33 mg/g and 82.6%, respectively, at an initial Ni(II) concentration of 100 mg/L, adsorption time of 30 min and no effect of the solution pH and adsorption temperature.

Lead and vanadium removal from a real industrial wastewater by gravitational settling/sedimentation and sorption onto Pinus sylvestris sawdust.

PubMed

Kaczala, F; Marques, M; Hogland, W

2009-01-01

Batch sorption with untreated Pinus sylvestris sawdust after settling/sedimentation phase to remove vanadium and lead from a real industrial wastewater was investigated using different adsorbent doses, initial pH, and contact time. The development of pH along the sorption test and a parallel investigation of metals release from sawdust in distilled water were carried out. In order to evaluate kinetic parameters and equilibrium isotherms, Lagergren first-order, pseudo-second-order, intra-particle diffusion and Freundlich models were explored. When the initial pH was reduced from 7.4 to 4.0, the sorption efficiency increased from 32% to 99% for Pb and from 43% to 95% for V. Whereas, V removal was positively correlated with the adsorbent dose, Pb removal was not. The sorption process was best described by pseudo-second-order kinetics. According to Freundlich parameters (K(f) and n) sawdust presented unfavourable intensity for sorption of V.

Biosorption of cadmium and chromium in duckweed Wolffia globosa.

PubMed

Upatham, E Suchart; Boonyapookana, Benjaporn; Kruatrachue, Maleeya; Pokethitiyook, Prayad; Parkpoomkamol, Krisna

2002-01-01

The biosorption of cadmium (Cd) and chromium (Cr) by using dried Wolffia globosa biomass were investigated using batch technique. The effects of concentration and pH solution on the adsorption isotherm were measured by determining the adsorption isotherm at initial metal concentrations from 10 to 400 mg/L and pH 4 to 7 for Cd, and pH 1.5 to 6 for Cr. The adsorption equilibria were found to follow Langmuir models. The maximum adsorption capacity (Xm) at pH 7 in W. globosa-Cd system was estimated to be 80.7 mg/g, while the maximum removal achieved at pH 4, pH 5, and pH 6 were 35.1, 48.8, and 65.4 mg/g, respectively. The Xm at pH 1.5 in W. globosa--Cr system was estimated to be 73.5 mg/g, while the maximum removal achieved at pH 3, pH 5, and pH 6 were 47.4, 33.1, and 12.9 mg/g, respectively. The effects of contact times on Cd and Cr sorption indicated that they were absorbed rapidly and more efficiently at lower concentrations.

Radial metal concentration profiles in trees growing on highly contaminated soils.

PubMed

Superville, Pierre-Jean; de Winter, Niels; Phung, Anh Tuan; Proix, Nicolas; Baeyens, Willy; Gao, Yue

2017-04-01

The soil around Metaleurop, a big smelter, is heavily contaminated by Zn, Pb, Cd and Cu. In order to compare the impact of different soil amendments on the metal availability to trees, the polluted soil section was divided in a reference parcel and two others with either sulfo-calcic or silico-aluminous ash amendments. Five different tree species were planted on the parcels and the uptake of heavy metals in these trees was studied. Total and labile metal fractions were assessed in each of the 3 parcels. The mobility and assimilation of the metals was highest in the non-amended, reference soil parcel which had the lowest pH, organic matter and carbonate content. In all soils, pH decreased while organic matter content and mobility of the metals increased over time. Highest bulk concentrations of trace metals were found in white willow trees (Salix alba L.). Laser ablation-ICPMS was used to study changes in metal accumulation over a period of 10 years after planting the trees. The radial metal profiles in the trunk core samples varied between elements and tree species, however, in all willow trees the radial Cd and Zn profiles were significantly correlated. Radial pollutant concentration patterns are discussed in terms of seasonal effects, health status, tree species and metal mobility in the soil. For Cd and Zn, the profiles were influenced by their mobility in the soils. In general, periodical patterns were observed for Pb. Cu concentration profiles were decreasing over time, with the strongest decrease in the initial growth period. Copyright © 2016 Elsevier Ltd. All rights reserved.

Preparation of Zeolite/Zinc Oxide Nanocomposites for toxic metals removal from water

NASA Astrophysics Data System (ADS)

Alswata, Abdullah A.; Ahmad, Mansor Bin; Al-Hada, Naif Mohammed; Kamari, Halimah Mohamed; Hussein, Mohd Zobir Bin; Ibrahim, Nor Azowa

This research work has proposed preparation of Zeolite/Zinc Oxide Nanocomposite (Zeolite/ZnO NCs) by using a co-precipitation method. Then, the prepared Nanocomposite has been tested for adsorption of Lead Pb (II) and Arsenic As (V) from aqueous solution under the room pressure and temperature. After that, the prepared adsorbent has been studied by several techniques. For adsorption process; the effect of the adsorbent masses, contact time, PH and initial metals concentration as well as, the kinetics and isotherm for adsorption process have been investigated. The results revealed that; ZnO nanoparticles (NPs) with average diameter 4.5 nm have successfully been loaded into Zeolite. The optimum parameters for the removal of the toxic metals 93% and 89% of Pb (II) and As (V), respectively, in 100 mg/L aqua solutions were pH4, 0.15 g and 30 min. According to the obtained results; pseudo second-order kinetic and Langmuir isotherm model have higher correlation coefficients and provided a better agreement with the experimental data. The prepared sorbent showed an economical and effective way to remove the heavy toxic metals due to its ambient operation conditions, low- consumption energy and facile regeneration method.

Soluble organic carbon and pH of organic amendments affect metal mobility and chemical speciation in mine soils.

PubMed

Pérez-Esteban, Javier; Escolástico, Consuelo; Masaguer, Alberto; Vargas, Carmen; Moliner, Ana

2014-05-01

We evaluated the effects of pH and soluble organic carbon affected by organic amendments on metal mobility to find out the optimal conditions for their application in the stabilization of metals in mine soils. Soil samples (pH 5.5-6.2) were mixed with 0, 30 and 60 th a(-1) of sheep-horse manure (pH 9.4) and pine bark compost (pH 5.7). A single-step extraction procedure was performed using 0.005 M CaCl2 adjusted to pH 4.0-7.0 and metal speciation in soil solution was simulated using NICA-Donnan model. Sheep-horse manure reduced exchangeable metal concentrations (up to 71% Cu, 75% Zn) due to its high pH and degree of maturity, whereas pine bark increased them (32% Cu, 33% Zn). However, at increasing dose and hence pH, sheep-horse manure increased soluble Cu because of higher soluble organic carbon, whereas soluble Cu and organic carbon increased at increasing dose and correspondingly decreasing pH in pine bark and non-amended treatments. Near the native pH of these soils (at pH 5.8-6.3), with small doses of amendments, there was minimum soluble Cu and organic carbon. Pine bark also increased Zn solubility, whereas sheep-horse manure reduced it as soluble Zn always decreased with increasing pH. Sheep-horse manure also reduced the proportion of free metals in soil solution (from 41% to 4% Cu, from 97% to 94% Zn), which are considered to be more bioavailable than organic species. Sheep-horse manure amendment could be efficiently used for the stabilization of metals with low risk of leaching to groundwater at low doses and at relatively low pH, such as the native pH of mine soils. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of ageing on the availability of heavy metals in soils amended with compost and biochar: evaluation of changes in soil and amendment properties.

PubMed

Venegas, A; Rigol, A; Vidal, M

2016-10-01

Remediation strategies using soil amendments should consider the time dependence of metal availability to identify amendments that can sustainably reduce available pollutant concentrations over time. Drying-wetting cycles were applied on amendments, soils and soil + amendment mixtures, to mimic ageing at field level and investigate its effect on extractable Cd, Cu, Ni, Pb and Zn concentrations from three contaminated soils. The amendments investigated were municipal waste organic compost and biochars. The amendments, soils and mixtures were characterised by their physicochemical properties at different ageing times. The amendments were also characterised in terms of sorption capacity for Cd and Cu. The sorption capacity and the physicochemical properties of the amendments remained constant over the period examined. When mixed with the soils, amendments, especially the compost, immediately reduced the extractable metals in the soils with low pH and acid neutralisation capacity, due to the increase in pH and buffering capacity of the mixtures. The amendments had a relatively minor impact on the metal availability concentrations for the soil with substantially high acid neutralisation capacity. The most important changes in extractable metal concentrations were observed at the beginning of the experiments, ageing having a minor effect on metal concentrations when compared with the initial effect of amendments.

Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

PubMed

Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

2009-06-15

In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

Metal availability and bio-accessibility in water-logged soils: in vitro experiments.

NASA Astrophysics Data System (ADS)

Florido, M. C.; Madrid, F.; Madrid, L.; Ajmone-Marsan, F.

2010-05-01

Reducing conditions of submerged soils were simulated in vitro by keeping various soil samples for various times of reaction (between 1 and 15 days) in sealed flasks and N2 atmosphere under an aqueous solution, 0.01 M CaCl2 containing 1 g/l glucose. Surface samples of soils from urban green areas of Ljubljana (LJU), Torino (TOR) and Sevilla, were chosen. In the latter case, two samples of the same soil were included, before (SE-0) and after (SE-8) receiving a composted biosolid (two yearly doses of 80000 kg/ha) obtained from sewage sludge, often used as amendment by the Parks & Gardens Service of the local Government. A fifth soil (QUE) was chosen from the area affected by an accident where 2 million m3 of metal-rich mine tailings were spilled over the Guadiamar river (SW Spain) and its riparian areas. This highly polluted soil was included for comparison. Values of Eh, pH and several metal concentrations were determined in the solution after each time, and metal availability and bio-accessibility were estimated in the soils after treatment. The metals studied were Fe, Mn and some of those called 'urban' metals, namely Cu, Pb and Zn. The solution pH for LJU, TOR and SE-0 was slightly acidified in the first days and increased steadily afterwards. In contrast, QUE and SE-8 show pH increases from the beginning and a constant pH after 4-8 days. This agrees with the expected H+ consumption during reduction. Most soils show strong initial Eh decreases, subsequent slower increases up to 5-8 days and slow decreases afterwards. Solution Fe and Mn showed significant increases throughout the experiment, and Pb showed slight increases only up to 4 days. In contrast, other metals showed non-significant changes, and very low amounts were dissolved during the treatment. However, the amounts of available and, especially, bio-accessible urban metals in the solid phases were significantly increased by the treatment. Such increases may cause a greater leaching of metals to the water table or a greater uptake of potentially toxic metals. In the case of ornamental sites, playgrounds and other recreational areas, such increases can have a direct significance on public health through a hand-to-mouth transfer. The observed increases are significant even in soils with not very high metal contents, as it is the case of LJU or SE samples.

Speciation and transformation of heavy metals during vermicomposting of animal manure.

PubMed

Lv, Baoyi; Xing, Meiyan; Yang, Jian

2016-06-01

This work was conducted to evaluate the effects of vermicomposting on the speciation and mobility of heavy metals (Zn, Pb, Cr, and Cu) in cattle dung (CD) and pig manure (PM) using tessier sequential extraction method. Results showed that the pH, total organic carbon and C/N ratio were reduced, while the electric conductivity and humic acid increased after 90days vermicomposting. Moreover, the addition of earthworm could accelerate organic stabilization in vermicomposting. The total heavy metals in final vermicompost from CD and PM were higher than the initial values and the control without worms. Sequential extraction indicated that vermicomposting decreased the migration and availability of heavy metals, and the earthworm could reduce the mobile fraction, while increase the stable fraction of heavy metals. Furthermore, these results indicated that vermicomposting played a positive role in stabilizing heavy metals in the treatment of animal manure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer

DOEpatents

Adzic, Radoslav; Harris, Alexander

2014-04-15

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by a surface preparation process involving immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing a suitable quantity of non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means. The nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. The process can be controlled and repeated to obtain a desired film coverage. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

Equilibrium and kinetic modelling of cadmium (II) biosorption by Dried Biomass Aphanothece sp. from aqueous phase

NASA Astrophysics Data System (ADS)

Awalina; Harimawan, A.; Haryani, G. S.; Setiadi, T.

2017-05-01

The Biosorption of cadmium (II) ions on dried biomass of Aphanothece sp.which previously grown in a photobioreactor system with atmospheric carbon dioxide fed input, was studied in a batch system with respect to initial pH, biomass concentration, contact time, and temperature. The biomass exhibited the highest cadmium (II) uptake capacity at 30ºC, initial pH of 8.0±0.2 in 60 minute and initial cadmium (II) ion concentration of 7.76 mg/L. Maximum biosorption capacities were 16.47 mg/g, 54.95 mg/g and 119.05 mg/g at range of initial cadmium (II) 0.96-3.63 mg/L, 1.99-8.10 mg/L and 6.48-54.38 mg/L, respectively. Uptake kinetics follows the pseudo-second order model while equilibrium is best described by Langmuir isotherm model. Isotherms have been used to determine thermodynamic parameter process (free energy change, enthalpy change and entropy change). FTIR analysis of microalgae biomass revealed the presence of amino acids, carboxyl, hydroxyl, sulfhydryl and carbonyl groups, which are responsible for biosorption of metal ions. During repeated sorption/desorption cycles, the ratio of Cd (II) desorption to biosorption decreased from 81% (at first cycle) to only 27% (at the third cycle). Nevertheless, due to its higher biosorption capability than other adsorbent, Aphanothece sp appears to be a good biosorbent for removing metal Cd (II) ions from aqueous phase.

Synthesis and molecular structures of phenylamides of magnesium, calcium, strontium, and barium--from molecular to polymeric structures.

PubMed

Gärtner, Martin; Görls, Helmar; Westerhausen, Matthias

2007-09-03

Several preparative procedures for the synthesis of the THF complexes of the alkaline earth metal bis(phenylamides) of Mg (1), Ca (2), Sr (3), and Ba (4) are presented such as metalation of aniline with strontium and barium, metathesis reactions of MI2 with KN(H)Ph, and metalation of aniline with arylcalcium compounds or dialkylmagnesium. The THF content of these compounds is rather low and an increasing aggregation is observed with the size of the metal atom. Thus, tetrameric [(THF)2Ca{mu-N(H)Ph}2]4 (2) and polymeric [(THF)2Sr{mu-N(H)Ph}2]infinity and {[(THF)2Ba{mu-N(H)Ph}2]2[(THF)Ba{mu-N(H)Ph}2]2}infinity show six-coordinate metal atoms with increasing interactions to the pi systems of the phenyl groups with increasing the radius of the alkaline earth metal atom.

Mechanistic study of lead desorption during the leaching process of ion-absorbed rare earths: pH effect and the column experiment.

PubMed

Tang, Jie; Xue, Qiang; Chen, Honghan; Li, Wenting

2017-05-01

High concentrations of ammonium sulfate, often used in the in situ mining process, can result in a decrease of pH in the environment and dissolution of rare earth metals. Ammonium sulfate can also cause desorption of toxic heavy metals, leading to environmental and human health implications. In this study, the desorption behavior and fraction changes of lead in the ion-absorbed rare earth ore were studied using batch desorption experiments and column leaching tests. Results from batch desorption experiments showed that the desorption process of lead included fast and slow stages and followed an Elovich model well. The desorption rate and the proportion of lead content in the solution to the total lead in the soil were observed to increase with a decrease in the initial pH of the ammonium sulfate solution. The lead in soil included an acid-extractable fraction, reducible fraction, oxidizable fraction, and a residual fraction, with the predominant fractions being the reducible and acid-extractable fractions. Ninety-six percent of the extractable fraction in soil was desorbed into solution at pH = 3.0, and the content of the reducible fraction was observed to initially increase (when pH >4.0) and then decrease (when pH <4.0) with a decrease in pH. Column leaching tests indicated that the content of lead in the different fractions of soil followed the trend of reducible fraction > oxidizable fraction > acid-extractable fraction > residual fraction after the simulating leaching mining process. The change in pH was also found to have a larger influence on the acid-extractable and reducible fractions than the other two fractions. The proportion of the extractable fraction being leached was ca. 86%, and the reducible fraction was enriched along the migration direction of the leaching liquid. These results suggest that certain lead fractions may desorb again and contaminate the environment via acid rain, which provides significant information for environmental assessment and remediation after mining process. Graphical abstract ᅟ.

Lead removal by Spirulina platensis biomass.

PubMed

Al-Homaidan, Ali A; Al-Abbad, Aljawharah F; Al-Hazzani, Amal A; Al-Ghanayem, Abdullah A; Alabdullatif, Jamila A

2016-01-01

In this investigation, we report on the biosorption of Pb (II) from aqueous solutions by the nonliving biomass of the micro-alga (cyanobacterium) Spirulina platensis. Propagation of the micro-alga was carried out in outside oblong raceway ponds. The biomass was cleaned, dried and used for the investigation. The effects of pH, adsorbent dose, temperature, initial concentration of Pb (II), and contact time on the adsorption of lead by the dry biomass were studied. The experiments were carried out in 250 ml conical flasks containing 100 ml of test solutions using an orbital incubator at 150 rpm. Concentrations of the metal before and after the experiments were measured using Atomic Absorption Spectrophotometer. Very high levels of Pb (II) removal (>91%) were obtained. The optimum conditions for maximal adsorption by S. platensis were found to be pH 3; 2 g of adsorbent dose; incubation at 26°C; 100 mg/l of lead initial concentration and 60 minutes of contact time. The experimental data fitted well with Freundlich isotherm equation with R(2) values greater than 0.97. Based on our results, we recommend the utilization of S. platensis biomass for heavy metal removal from aqueous solutions.

Growth and heavy metal removal by Klebsiella aerogenes at different pH and temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al-Shahwani, M.F.; Jazrawi, S.F.; Al-Rawi, E.H.

1984-01-01

A strain of Klebsiella aerogenes isolated from Rustamiyah Station for treatment of wastewater was examined for its ability to grow in a media supplemented with maximum tolerance concentrations of Pb/sup + +/, Zn/sup + +/, Ni/sup + +/, and Cd/sup + +/, separately, at different temperatures and initial pH. The results indicated that at 28/sup 0/C during the first 24 hr, Pb/sup + +/ and Ni/sup + +/ had no effect on the growth of the bacteria, while the presence of Zn/sup + +/ and Cd/sup + +/ decreased the cell count. The growth reached a maximum level after themore » second day and started to decrease gradually. The bacterial count at 37/sup 0/C was less than that at 28/sup 0/C. No bacterial multiplication occurred at 44/sup 0/C. There was little difference between heavy metal removal at 28 and 37/sup 0/C. At 44/sup 0/C, little removal took place. In general, slightly acidic or neutral medium was better for both bacterial growth and metal removal.« less

Functionalized dithiocarbamate chelating resin for the removal of Co2+ from simulated wastewater

NASA Astrophysics Data System (ADS)

Shi, Xuewei; Fu, Linwei; Wu, Yanyang; Zhao, Huiling; Zhao, Shuangliang; Xu, Shouhong

2017-12-01

Industrial wastewater that contains trace amounts of heavy metal ions is often seen in petrochemical industry. While this wastewater can not be directly discharged, it is difficult to treat due to the low concentration of metal ions. Introducing chelating reagents into this wastewater for selective ion adsorption, followed by a mechanical separation process, provides an appealing solution. Toward the success of this technology, the development of effective chelating resins is of key importance. In the present work, a chelating resin containing amino and dithiocarbamate groups was reported for the removal of Co(II) metal ions in trace concentrations from simulated wastewater. By investigating the adsorption performance of the chelating resin at different solution pH values, adsorbent dosages, contact time, initial ion concentrations, and adsorption temperatures, the maximum adsorption capacity of the resin for Co(II) was identified to be 24.89 mg g-1 for a 2 g L-1 adsorbent dosage and a pH value of 5. After four adsorption-desorption cycles, 97% of the adsorption capacity of the resin was maintained. The adsorption kinetics and thermodynamics were analyzed and discussed as well.

A tropical sediment toxicity test using the dipteran Chironomus crassiforceps to test metal bioavailability with sediment pH change in tropical acid-sulfate sediments.

PubMed

Peck, Mika R; Klessa, David A; Baird, Donald J

2002-04-01

The wetlands of the Magela floodplain of northern Australia, which is the major sink for dissolved metals transported in the Magela Creek system, contain acid-sulfate sediments. The rewetting of oxidized acid-sulfate soil each wet season produces acidic pulses that have the potential to alter the bioavailability of sediment-associated metal contaminants. Acute toxicity tests (72-h mean lethal concentration [LC50]) using the tropical chironomid Chironomus crassiforceps Kieffer showed that copper toxicity decreased from 0.64 mg/L at pH 6 to 2.30 mg/L at pH 4. Uranium toxicity showed a similar trend (36 mg/L at pH 6 and 58 mg/L at pH 4). Sediment toxicity tests developed using C. crassiforceps also showed that both metals were less toxic at the lower sediment pH with pore-water copper toxicity having a lowest-observed-effect concentration of 4.73 mg/L at pH 4 compared to 1.72 mg/L at pH 6. However, a lower pH increased pore-water metal concentrations and overlying water concentrations in bioassays. Hydrogen ion competition on metal receptor sites in C. crassiforceps was proposed to explain the decrease in toxicity in response to increased H+ activity. This study highlights the need to consider site-specific physicochemical conditions before applying generic risk assessment methods.

Biosorption kinetics of heavy metals by leaf biomass of Jatropha curcas in single and multi-metal system.

PubMed

Rawat, Anand Prabha; Giri, Krishna; Rai, J P N

2014-03-01

Biosorption of Cu(2+), Zn(2+), and Cr(6+) from aqueous solutions by leaf biomass of Jatropha curcas was investigated as a function of biomass concentration, initial metal ion concentration, contact time, and pH of the solution systematically. The aim of this study was to optimize biosorption process and find out a suitable kinetic model for the metal removal in single and multi-metal system. The experimental data were analyzed using two sorption kinetic models, viz., pseudo-first- and pseudo-second-order equations, to determine the best fit equation for the biosorption of metal ions Cu(2+), Zn(2+), and Cr(6+) onto the leaf biomass of J. curcas in different metal systems. The experimental data fitted well the pseudo-second-order equation and provided the best correlation for the biosorption process. The findings of the present investigation revealed that J. curcas leaf biomass was an eco-friendly and cost-effective biosorbent for the removal of heavy metal ions from wastewater.

Lead sorption by waste biomass of hazelnut and almond shell.

PubMed

Pehlivan, Erol; Altun, Türkan; Cetin, Serpil; Iqbal Bhanger, M

2009-08-15

The potential to remove Pb(2+) ion from aqueous solutions using the shells of hazelnut (HNS) (Corylus avellana) and almond (AS) (Prunus dulcis) through biosorption was investigated in batch experiments. The main parameters influencing Pb(2+) ion sorption on HNS and AS were: initial metal ion concentration, amount of adsorbent, contact time and pH value of solution. The influences of initial Pb(2+) ion concentration (0.1-1.0mM), pH (2-9), contact time (10-240 min) and adsorbent amount (0.1-1.0 g) have been investigated. Equilibrium isotherms have been measured and modelled. Adsorption of Pb(2+) ions was in all cases pH-dependent showing a maximum at equilibrium pH values between 6.0 and 7.0, depending on the biomaterial, that corresponded to equilibrium pH values of 6.0 for HNS and 7.0 for AS. The equilibrium sorption capacities of HNS and AS were 28.18 and 8.08 mg/g for lead, respectively after equilibrium time of 2h. The adsorption data fit well with the Langmuir isotherm model and the experimental result inferred that adsorption, chelation and ion exchange are major adsorption mechanisms for binding Pb(2+) ion to the sorbents.

Polishing of treated palm oil mill effluent (POME) from ponding system by electrocoagulation process.

PubMed

Bashir, Mohammed J K; Mau Han, Tham; Jun Wei, Lim; Choon Aun, Ng; Abu Amr, Salem S

2016-01-01

As the ponding system used to treat palm oil mill effluent (POME) frequently fails to satisfy the discharge standard in Malaysia, the present study aimed to resolve this problem using an optimized electrocoagulation process. Thus, a central composite design (CCD) module in response surface methodology was employed to optimize the interactions of process variables, namely current density, contact time and initial pH targeted on maximum removal of chemical oxygen demand (COD), colour and turbidity with satisfactory pH of discharge POME. The batch study was initially designed by CCD and statistical models of responses were subsequently derived to indicate the significant terms of interactive process variables. All models were verified by analysis of variance showing model significances with Prob > F < 0.01. The optimum performance was obtained at the current density of 56 mA/cm(2), contact time of 65 min and initial pH of 4.5, rendering complete removal of colour and turbidity with COD removal of 75.4%. The pH of post-treated POME of 7.6 was achieved, which is suitable for direct discharge. These predicted outputs were subsequently confirmed by insignificant standard deviation readings between predicted and actual values. This optimum condition also permitted the simultaneous removal of NH3-N, and various metal ions, signifying the superiority of the electrocoagulation process optimized by CCD.

Polyaspartate extraction of cadmium ions from contaminated soil: Evaluation and optimization using central composite design.

PubMed

Mu'azu, Nuhu Dalhat; Haladu, Shamsuddeen A; Jarrah, Nabeel; Zubair, Mukarram; Essa, Mohammad H; Ali, Shaikh A

2018-01-15

The occurrences of heavy metal contaminated sites and soils and the need for devising environmentally friendly solutions have become global issues of serious concern. In this study, polyaspartate (a highly biodegradable agent) was synthesized using L-Aspartic acid via a new modified thermal procedure and employed for extraction of cadmium ions (Cd) from contaminated soil. Response surface methodology approach using 3 5 full faced centered central composite design was employed for modeling, evaluating and optimizing the influence of polyaspartate concentration (36-145mM), polyaspartate/soil ratio (5-25), initial heavy metal concentration (100-500mg/kg), initial pH (3-6) and extraction time (6-24h) on Cd ions extracted into the polyaspartate solution and its residual concentration in the treated soil. The Cd extraction efficacy obtained reached up to 98.8%. Increase in Cd extraction efficiency was associated with increase in the polyaspartate and Cd concentration coupled with lower polyaspertate/soil ratio and initial pH. Under the optimal conditions characterized with minimal utilization of the polyaspartate and high Cd ions removal, the extractible Cd in the polyaspartate solution reached up to 84.4mg/L which yielded 85% Cd extraction efficacy. This study demonstrates the suitability of using polyaspartate as an effective environmentally friendly chelating agent for Cd extraction from contaminated soils. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of pH on frog gustatory responses to chloride salts of alkali-metal and alkali-earth-metal.

PubMed

Kumai, T; Nomura, H

1980-01-01

The pH effects on frog gustatory responses to alkali-metal and alkali-earth-metal chloride salts were examined using single fungi-form papilla preparations. Responses to 0.1-0.5 M NaCl were clearly dependent upon the pH of the stimulating solutions. The responses increased as the pH decreased from 6.5 to 4.5 and were almost completely suppressed at pH's above 6.5. There was no significant difference in the pH dependency of the response among alkali-metal chlorides. HCl solutions elicited only a poor response under conditions in which the water response was suppressed by the simultaneous presence of a low NaCl concentration. Responses to alkali-earth-metal chlorides varied in their pH dependency. Response to CaCl2 was slightly affected by pH changes from 4.5 to 9.0, response to SrCl2 was considerably suppressed in the alkaline region, and responses to BaCl2 and MgCl2 were strongly suppressed at pH's above 6.5. BeCl2 solutions showed less marked stimulating effects over the pH range tested. The differences in pH dependency described above suggest the existence of two kinds of receptor sites, one being pH-insensitive sites responsible for the calcium response and the other pH-sensitive sites responsible for the sodium response. A cross-adaptation test appeared to support this possibility. Assuming that the pH effect mentioned is related to changes in the state of ionization of the receptor molecule, the pKa of the ionizable group responsible for the sodium response was determined to be approximately 5.5.

Field scale remediation of mine wastes at an abandoned gold mine, Australia II: Effects on plant growth and groundwater

NASA Astrophysics Data System (ADS)

Maddocks, Greg; Lin, Chuxia; McConchie, David

2009-05-01

This second paper reports the results of plant growth, plant mortality, plant leaf tissue metal and salt concentrations and leachate quality monitoring from lysimeters in four large field trial treatments established on sulfidic waste rock/soil that was used for haul road construction at a closed gold mine in Australia. The TerraB™, lime and clay treatments allowed good tree growth of four Eucalypt species, compared to the control. There was no statistical difference in tree growth between the TerraB™, lime or clay treatments over the 2 years of monitoring in this paper. However, the growth of one tree species was poor in the TerraB™ treatment. Leaf tissue metal and major ion data are also presented. Leachate pH in the control became increasingly acidic (pH 4.57-3.95). The addition of Ca(OH)2 and biosolids led to an initial increase in leachate pH, compared to the control; however, this has decreased over the duration of the study (pH 5.37-4.89) and may affect the sustainable growth of plants in the future. In the TerraB™ and biosolids treatment leachate pH increased to 6.92 after the first rainfall event and continued to increase over the duration of the study to pH 7.4 after 24 months. After 24 months average heavy metal leachate concentrations (mg/L) in the lysimeters for Al, Cd, Cu, Mn and Zn were, control: 32.55, 5.67, 12.71, 39.29, 121.80, TerraB™: 0.07, 0.02, 0.07, 0.57, 0.23, and lime: 2.19, 1.19, 2.33, 3.6, 28.4. No leachate was available for collection from the clay treatment indicating that this technique was functioning in terms of minimizing the infiltration of water into the mine soil.

Comparative studies on adsorptive removal of heavy metal ions by biosorbent, bio-char and activated carbon obtained from low cost agro-residue.

PubMed

Kırbıyık, Çisem; Pütün, Ayşe Eren; Pütün, Ersan

2016-01-01

In this study, Fe(III) and Cr(III) metal ion adsorption processes were carried out with three adsorbents in batch experiments and their adsorption performance was compared. These adsorbents were sesame stalk without pretreatment, bio-char derived from thermal decomposition of biomass, and activated carbon which was obtained from chemical activation of biomass. Scanning electron microscopy and Fourier transform-infrared techniques were used for characterization of adsorbents. The optimum conditions for the adsorption process were obtained by observing the influences of solution pH, adsorbent dosage, initial solution concentration, contact time and temperature. The optimum adsorption efficiencies were determined at pH 2.8 and pH 4.0 for Fe(III) and Cr(III) metal ion solutions, respectively. The experimental data were modelled by different isotherm models and the equilibriums were well described by the Langmuir adsorption isotherm model. The pseudo-first-order, pseudo-second-order kinetic, intra-particle diffusion and Elovich models were applied to analyze the kinetic data and to evaluate rate constants. The pseudo-second-order kinetic model gave a better fit than the others. The thermodynamic parameters, such as Gibbs free energy change ΔG°, standard enthalpy change ΔH° and standard entropy change ΔS° were evaluated. The thermodynamic study showed the adsorption was a spontaneous endothermic process.

Water quality of Tampa Bay, Florida, June 1972-May 1976

USGS Publications Warehouse

Goetz, Carole L.; Goodwin, Carl R.

1980-01-01

A comprehensive assessment of the water quality of Tampa Bay, Florida, was initiated in 1970 to provide background information to evaluate the effects of widening and deepening the ship channel to the port of Tampa. This report provides results of water-quality sampling in the bay from 1972 to 1976, prior to dredging. Measurements of temperature, dissolved oxygen, pH, turbidity, specific conductance, biochemical oxygen demand, and total organic carbon were made as well as measurements for several nutrient, metal, and pesticide parameters. Many parameters were measured at as many as three points in the vertical. These data indicate that Tampa Bay is well-mixed vertically with little density stratification. Time histories of average temperature, dissolved oxygen, pH, turbidity, specific conductance and nutrient values within four subareas of Tampa Bay are given to reveal seasonal or other trends during the period of record. Temperature, dissolved oxygen, pH, turbidity, specific conductance, nutrient, biochemical oxygen demand, total organic carbon, and metal data are also presented as areal distributions. Nutrient concentrations were generally higher in Hillsborough Bay than in other sub-areas of Tampa Bay. Biochemical oxygen demand, total organic carbon, and total organic nitrogen distribution patterns show regions of highest concentrations to be along bay shorelines near population centers. Of the metals analyzed, all were present in concentrations of less than 1 milligram per liter. (USGS)

Papaya Seeds as A Low-Cost Sorbent for Removing Cr(VI) from The Aqueous Solution

NASA Astrophysics Data System (ADS)

Rahmawati, Atik; Marwoto, Putut; Karunia Z, Anita

2016-08-01

The presence of chromium (VI) contaminants and their toxicity in aqueous streams important environmental problems. Adsorption is one of the effective techniques that can be used for removing metal from wastewater. This research was initiated by preparing sorbent from papaya seeds and determining its functional group contents by using FT-IR. The adsorption process was carried out in a batch method. The study of adsorption aspects involved the pH, initial Cr (VI) concentration and contact time between Cr (VI) and sorbent. FT IR analysis results showed that the main functional groups are carbonyl, hydroxyl, and carboxylic. It was also found that the effective pH for Cr (VI) uptake is 2.0 and increasing contact time would increase the Cr (VI) uptake. In addition, the equilibrium was reached after 40 minutes interaction and the increase of initial chromium (VI) concentration would increase the sorbent uptake percentage. All these results indicated that papaya seed is a potential sorbent for removing Cr (VI) from aqueous solutions.

Structural response of phyllomanganates to wet aging and aqueous Mn(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates weremore » studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

Structural response of phyllomanganates to wet aging and aqueous Mn(II)

DOE PAGES

Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

2016-08-06

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates weremore » studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

Electrocoagulation and nanofiltration integrated process application in purification of bilge water using response surface methodology.

PubMed

Akarsu, Ceyhun; Ozay, Yasin; Dizge, Nadir; Elif Gulsen, H; Ates, Hasan; Gozmen, Belgin; Turabik, Meral

Marine pollution has been considered an increasing problem because of the increase in sea transportation day by day. Therefore, a large volume of bilge water which contains petroleum, oil and hydrocarbons in high concentrations is generated from all types of ships. In this study, treatment of bilge water by electrocoagulation/electroflotation and nanofiltration integrated process is investigated as a function of voltage, time, and initial pH with aluminum electrode as both anode and cathode. Moreover, a commercial NF270 flat-sheet membrane was also used for further purification. Box-Behnken design combined with response surface methodology was used to study the response pattern and determine the optimum conditions for maximum chemical oxygen demand (COD) removal and minimum metal ion contents of bilge water. Three independent variables, namely voltage (5-15 V), initial pH (4.5-8.0) and time (30-90 min) were transformed to coded values. The COD removal percent, UV absorbance at 254 nm, pH value (after treatment), and concentration of metal ions (Ti, As, Cu, Cr, Zn, Sr, Mo) were obtained as responses. Analysis of variance results showed that all the models were significant except for Zn (P > 0.05), because the calculated F values for these models were less than the critical F value for the considered probability (P = 0.05). The obtained R(2) and Radj(2) values signified the correlation between the experimental data and predicted responses: except for the model of Zn concentration after treatment, the high R(2) values showed the goodness of fit of the model. While the increase in the applied voltage showed negative effects, the increases in time and pH showed a positive effect on COD removal efficiency; also the most effective linear term was found as time. A positive sign of the interactive coefficients of the voltage-time and pH-time systems indicated synergistic effect on COD removal efficiency, whereas interaction between voltage and pH showed an antagonistic effect.

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy

PubMed Central

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-01-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER. PMID:27034988

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

PubMed

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-03-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

Simultaneous recovery of Ni and Cu from computer-printed circuit boards using bioleaching: statistical evaluation and optimization.

PubMed

Arshadi, M; Mousavi, S M

2014-12-01

Computer printed circuit boards (CPCBs) have a rich metal content and are produced in high volume, making them an important component of electronic waste. The present study used a pure culture of Acidithiobacillus ferrooxidans to leach Cu and Ni from CPCBs waste. The adaptation phase began at 1g/l CPCBs powder with 10% inoculation and final pulp density was reached at 20g/l after about 80d. Four effective factors including initial pH, particle size, pulp density, and initial Fe(3+) concentration were optimized to achieve maximum simultaneous recovery of Cu and Ni. Their interactions were also identified using central composite design in response surface methodology. The suggested optimal conditions were initial pH 3, initial Fe(3+) 8.4g/l, pulp density 20g/l and particle size 95μm. Nearly 100% of Cu and Ni were simultaneously recovered under optimum conditions. Finally, bacterial growth characteristics versus time at optimum conditions were plotted. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of temperature on copper, iron and lead leaching from e-waste using citrate solutions.

PubMed

Torres, Robinson; Segura-Bailón, Brenda; Lapidus, Gretchen T

2018-01-01

E-waste is a potential source of large quantities of metals. The ability of citrate solutions to recover base metals from these materials has been demonstrated. In the present study, the effect of the temperature on base metal leaching capacity by the citrate solutions is determined. The material employed consisted of a mechanically prepared, gravity concentrated e-waste, with a metallic content greater than 90%. The leaching conditions were selected based on previous research performed by the authors (0.5 M sodium citrate, pH 4.5 and 20 g per liter e-waste concentrate). Leaching tests were performed at temperatures between 0° and 70 °C. The initial leaching rates for the three metals increased with temperature. However, these tapered off with time for temperatures above 30 °C, which can be associated to citrate destruction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Elucidation of metal-ion accumulation induced by hydrogen bonds on protein surfaces by using porous lysozyme crystals containing Rh(III) ions as the model surfaces.

PubMed

Ueno, Takafumi; Abe, Satoshi; Koshiyama, Tomomi; Ohki, Takahiro; Hikage, Tatsuo; Watanabe, Yoshihito

2010-03-01

Metal-ion accumulation on protein surfaces is a crucial step in the initiation of small-metal clusters and the formation of inorganic materials in nature. This event is expected to control the nucleation, growth, and position of the materials. There remain many unknowns, as to how proteins affect the initial process at the atomic level, although multistep assembly processes of the materials formation by both native and model systems have been clarified at the macroscopic level. Herein the cooperative effects of amino acids and hydrogen bonds promoting metal accumulation reactions are clarified by using porous hen egg white lysozyme (HEWL) crystals containing Rh(III) ions, as model protein surfaces for the reactions. The experimental results reveal noteworthy implications for initiation of metal accumulation, which involve highly cooperative dynamics of amino acids and hydrogen bonds: i) Disruption of hydrogen bonds can induce conformational changes of amino-acid residues to capture Rh(III) ions. ii) Water molecules pre-organized by hydrogen bonds can stabilize Rh(III) coordination as aqua ligands. iii) Water molecules participating in hydrogen bonds with amino-acid residues can be replaced by Rh(III) ions to form polynuclear structures with the residues. iv) Rh(III) aqua complexes are retained on amino-acid residues through stabilizing hydrogen bonds even at low pH (approximately 2). These metal-protein interactions including hydrogen bonds may promote native metal accumulation reactions and also may be useful in the preparation of new inorganic materials that incorporate proteins.

Acute toxicity of heavy metals to acetate-utilizing mixed cultures of sulfate-reducing bacteria: EC100 and EC50.

PubMed

Utgikar, V P; Chen, B Y; Chaudhary, N; Tabak, H H; Haines, J R; Govind, R

2001-12-01

Acid mine drainage from abandoned mines and acid mine pit lakes is an important environmental concern and usually contains appreciable concentrations of heavy metals. Because sulfate-reducing bacteria (SRB) are involved in the treatment of acid mine drainage, knowledge of acute metal toxicity levels for SRB is essential for the proper functioning of the treatment system for acid mine drainage. Quantification of heavy metal toxicity to mixed cultures of SRB is complicated by the confounding effects of metal hydroxide and sulfide precipitation, biosorption, and complexation with the constituents of the reaction matrix. The objective of this paper was to demonstrate that measurements of dissolved metal concentrations could be used to determine the toxicity parameters for mixed cultures of sulfate-reducing bacteria. The effective concentration, 100% (EC100), the lowest initial dissolved metal concentrations at which no sulfate reduction is observed, and the effective concentration, 50% (EC50), the initial dissolved metal concentrations resulting in a 50% decrease in sulfate reduction, for copper and zinc were determined in the present study by means of nondestructive, rapid physical and chemical analytical techniques. The reaction medium used in the experiments was designed specifically (in terms of pH and chemical composition) to provide the nutrients necessary for the sulfidogenic activity of the SRB and to preclude chemical precipitation of the metals under investigation. The toxicity-mitigating effects of biosorption of dissolved metals were also quantified. Anaerobic Hungate tubes were set up (at least in triplicate) and monitored for sulfate-reduction activity. The onset of SRB activity was detected by the blackening of the reaction mixture because of formation of insoluble ferrous sulfide. The EC100 values were found to be 12 mg/L for copper and 20 mg/L for zinc. The dissolved metal concentration measurements were effective as the indicators of the effect of the heavy metals at concentrations below EC100. The 7-d EC50 values obtained from the difference between the dissolved metal concentrations for the control tubes (tubes not containing copper or zinc) and tubes containing metals were found to be 10.5 mg/L for copper and 16.5 mg/L for zinc. Measurements of the turbidity and pH, bacterial population estimations by means of a most-probable number technique, and metal recovery in the sulfide precipitate were found to have only a limited applicability in these determinations.

A new morphological approach for removing acid dye from leather waste water: preparation and characterization of metal-chelated spherical particulated membranes (SPMs).

PubMed

Şenay, Raziye Hilal; Gökalp, Safiye Meriç; Türker, Evren; Feyzioğlu, Esra; Aslan, Ahmet; Akgöl, Sinan

2015-03-15

In this study, p(HEMA-GMA) poly(hydroxyethyl methacrylate-co-glycidyl methacrylate) spherical particulated membranes (SPMs) were produced by UV-photopolymerization and the synthesized SPMs were coupled with iminodiacetic acid (IDA). Finally the novel SPMs were chelated with Cr(III) ions as ligand and used for removing acid black 210 dye. Characterizations of the metal-chelated SPMs were made by SEM, FTIR and swelling test. The water absorption capacities and acid dye adsorption properties of the SPMs were investigated and the results were 245.0, 50.0, 55.0 and 51.9% for p(HEMA), p(HEMA-GMA), p(HEMA-GMA)-IDA and p(HEMA-GMA)-IDA-Cr(III) SPMs respectively. Adsorption properties of the p(HEMA-GMA)-IDA-Cr(III) SPMs were investigated under different conditions such as different initial dye concentrations and pH. The optimum pH was observed at 4.3 and the maximum adsorption capacity was determined as 885.14 mg/g at about 8000 ppm initial dye concentration. The concentrations of the dyes were determined using a UV/Vis Spectrophotometer at a wavelength of 435 nm. Reusability of p(HEMA-GMA)-IDA-Cr(III) SPMs was also shown for five adsorption-desorption cycles without considerable decrease in its adsorption capacity. Finally, the results showed that the metal-chelated p(HEMA-GMA)-IDA SPMs were effective sorbent systems removing acid dye from leather waste water. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mineralogy and Geochemical Processes of Carbonate Mineral-rich Sulfide Mine Tailings, Zimapan, Mexico

NASA Astrophysics Data System (ADS)

McClure, R. J.; Deng, Y.; Loeppert, R.; Herbert, B. E.; Carrillo, R.; Gonzalez, C.

2009-12-01

Mining for silver, lead, zinc, and copper in Zimapan, Hidalgo State, Mexico has been ongoing since 1576. High concentrations of heavy metals have been found in several mine tailing heaps in the Zimapan area, with concentrations of arsenic observed as high as 28,690 mg/kg and levels of Pb as high as 2772 mg/kg. Unsecured tailings heaps and associated acid mine drainage has presented tremendous problems to revegetation, water quality, and dust emission control in the Zimapan area. Although acid mine drainage problems related to weathering of sulfide minerals have been extensively studied and are well known, the weathering products of sulfides in areas with a significant presence of carbonate minerals and their effect on the mobility of heavy metals warrant further study. Carbonate minerals are expected to neutralize sulfuric acid produced from weathering of sulfide minerals, however, in the Zimapan area localized areas of pH as low as 1.8 were observed within carbonate mineral-rich tailing heaps. The objectives of this study are to characterize (1) the heavy metal-containing sulfide minerals in the initial tailing materials, (2) the intermediate oxidation products of sulfide minerals within the carbonate-rich tailings, (3) chemical species of heavy metals within pH gradients between 1.8 and 8.2, the approximate natural pH of limestone, and (4) the mobility of soluble and colloidal heavy metals and arsenic within the carbonate-rich tailings. Representative mine tailings and their intermediate oxidation products have been sampled from the Zimapan area. Mineralogical characterization will be conducted with X-ray diffraction, infrared spectroscopy, electron microscopes and microprobes, and chemical methods. Chemical species will be extracted by selective dissolution methods. Preliminary results have identified calcite as the dominant mineral in the tailing heaps with a pH of 7, suggesting non-equilibrium with the acidic weathering products. Other minerals identified in the tailings include gypsum, quartz, pyrite, mica, talc, amphiboles, and feldspars. Oxidation products identified include copiapite as well as various iron oxides. Future results are expected to reveal most of the heavy metals to be adsorbed by or coprecipitate with iron oxides, with most of the oxidized arsenic staying in the soluble form. The mobility of the colloidal form of the oxides and associated heavy metals within the carbonate mineral-rich tailings need additional study.

Removal of trace metal contaminants from potable water by electrocoagulation.

PubMed

Heffron, Joe; Marhefke, Matt; Mayer, Brooke K

2016-06-21

This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency.

Removal of trace metal contaminants from potable water by electrocoagulation

NASA Astrophysics Data System (ADS)

Heffron, Joe; Marhefke, Matt; Mayer, Brooke K.

2016-06-01

This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency.

The sorption of lead, cadmium, copper and zinc ions from aqueous solutions on a raw diatomite from Algeria.

PubMed

Safa, Messaouda; Larouci, Mohammed; Meddah, Boumediene; Valemens, Pierre

2012-01-01

The adsorption of Cu(2+), Zn(2+), Cd(2+) and Pb(2+) ions from aqueous solution by Algerian raw diatomite was studied. The influences of different sorption parameters such as contact pH solution, contact time and initial metal ions concentration were studied to optimize the reaction conditions. The metals ions adsorption was strictly pH dependent. The maximum adsorption capacities towards Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were 0.319, 0.311, 0.18 and 0.096 mmol g(-1), respectively. The kinetic data were modelled using the pseudo-first-order and pseudo-second-order kinetic equations. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analysed using the Langmuir and the Freundlich isotherms; the results showed that the adsorption equilibrium was well described by both model isotherms. The negative value of free energy change ΔG indicates feasible and spontaneous adsorption of four metal ions on raw diatomite. According to these results, the high exchange capacities of different metal ions at high and low concentration levels, and given the low cost of the investigated adsorbent in this work, Algerian diatomite was considered to be an excellent adsorbent.

Carbonised jackfruit peel as an adsorbent for the removal of Cd(II) from aqueous solution.

PubMed

Inbaraj, B Stephen; Sulochana, N

2004-08-01

The fruit of the jack (Artocarpus heterophyllus) is one of the popular fruits in India, where the total area under this fruit is about 13,460 ha. A significant amount of peel (approximately 2,714-11,800 kg per tree per year) is discarded as agricultural waste, as apart from its use as a table fruit, it is popular in many culinary preparations. Treatment of jackfruit peel with sulphuric acid produced a carbonaceous product which was used to study its efficiency as an adsorbent for the removal of Cd(II) from aqueous solution. Batch experiments were performed as a function of process parameters; agitation time, initial metal concentration, adsorbent concentration and pH. Kinetic analyses made with Lagergren pseudo-first-order, Ritchie second-order and modified Ritchie second-order models showed better fits with modified Ritchie second-order model. The Langmuir-Freundlich (Sips equation) model best defined the experimental equilibrium data among the three isotherm models (Freundlich, Langmuir and Langmuir-Freundlich) tested. Taking a particular metal concentration, the optimum dose and pH required for the maximum metal removal was established. A complete recovery of the adsorbed metal ions from the spent adsorbent was achieved by using 0.01 M HCl.

Removal of Vanadium(III) and Molybdenum(V) from Wastewater Using Posidonia oceanica (Tracheophyta) Biomass

PubMed Central

Pennesi, Chiara; Totti, Cecilia; Beolchini, Francesca

2013-01-01

The use of dried and re-hydrated biomass of the seagrass Posidonia oceanica was investigated as an alternative and –low-cost biomaterial for removal of vanadium(III) and molybdenum(V) from wastewaters. Initial characterisation of this biomaterial identified carboxylic groups on the cuticle as potentially responsible for cation sorption, and confirmed the toxic-metal bioaccumulation. The combined effects on biosorption performance of equilibrium pH and metal concentrations were investigated in an ideal single-metal system and in more real-life multicomponent systems. There were either with one metal (vanadium or molybdenum) and sodium nitrate, as representative of high ionic strength systems, or with the two metals (vanadium and molybdenum). For the single-metal solutions, the optimum was at pH 3, where a significant proportion of vanadium was removed (ca. 70%) while there was ca. 40% adsorption of molybdenum. The data obtained from the more real-life multicomponent systems showed that biosorption of one metal was improved both by the presence of the other metal and by high ionic strength, suggesting a synergistic effect on biosorption rather than competition. There data ware used for the development of a simple multi-metal equilibrium model based on the non-competitive Langmuir approach, which was successfully fitted to experimental data and represents a useful support tool for the prediction of biosorption performance in such real-life systems. Overall, the results suggest that biomass of P. oceanica can be used as an efficient biosorbent for removal of vanadium(III) and molybdenum(V) from aqueous solutions. This process thus offers an eco-compatible solution for the reuse of the waste material of leaves that accumulate on the beach due to both human activities and to storms at sea. PMID:24204692

Remediation of lead-contaminated soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, R.W.; Shem, L.

1992-01-01

Excavation and transport of soil contaminated with heavy metals has generally been the standard remediation technique for treatment of heavy-metal-contaminated soils. This approach is not a permanent solution; moreover, off-site shipment and disposal of contaminated soil involves high expense, liability, and appropriate regulatory approval. Recently, a number of other techniques have been investigated for treating such contaminated sites, including flotation, solidification/stabilization, vitrification, and chemical extraction. This paper reports the results of a laboratory investigation determining the efficiency of using chelating agents to extract lead from contaminated soils. Lead concentrations in the soils ranged from 500 to 10,000 mg/kg. Ethylenediaminetetraacetic acidmore » (EDTA) and nitrilotriacetic acid (NTA) were examined for their potential extractive capabilities. Concentrations of the chelating agents ranged from 0.01 to 0.10 M. The pH of the suspensions in which the extractions were performed ranged from 4 to 12. Results showed that the removal of lead using NTA and water was ph-dependent, whereas the removal of lead using EDTA was ph-insensitive. Maximum removals of lead were 68.7%,19.1%, and 7.3% using EDTA, NTA, and water, respectively (as compared with initial lead concentrations).« less

Remediation of lead-contaminated soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, R.W.; Shem, L.

1992-09-01

Excavation and transport of soil contaminated with heavy metals has generally been the standard remediation technique for treatment of heavy-metal-contaminated soils. This approach is not a permanent solution; moreover, off-site shipment and disposal of contaminated soil involves high expense, liability, and appropriate regulatory approval. Recently, a number of other techniques have been investigated for treating such contaminated sites, including flotation, solidification/stabilization, vitrification, and chemical extraction. This paper reports the results of a laboratory investigation determining the efficiency of using chelating agents to extract lead from contaminated soils. Lead concentrations in the soils ranged from 500 to 10,000 mg/kg. Ethylenediaminetetraacetic acidmore » (EDTA) and nitrilotriacetic acid (NTA) were examined for their potential extractive capabilities. Concentrations of the chelating agents ranged from 0.01 to 0.10 M. The pH of the suspensions in which the extractions were performed ranged from 4 to 12. Results showed that the removal of lead using NTA and water was ph-dependent, whereas the removal of lead using EDTA was ph-insensitive. Maximum removals of lead were 68.7%,19.1%, and 7.3% using EDTA, NTA, and water, respectively (as compared with initial lead concentrations).« less

Banana peel: a green and economical sorbent for the selective removal of Cr(VI) from industrial wastewater.

PubMed

Memon, Jamil R; Memon, Saima Q; Bhanger, Muhammad I; El-Turki, Adel; Hallam, Keith R; Allen, Geoffrey C

2009-05-01

This study describes the use of banana peel, a commonly produced fruit waste, for the removal of Cr(VI) from industrial wastewater. The parameters pH, contact time, initial metal ion concentration, and temperature were investigated and the conditions resulting in rapid and efficient adsorption (95% within 10 min) were determined. The binding of metal ions was found to be pH dependent with the optimal sorption occurring at pH 2. The retained species were eluted with 5 mL of 2M H(2)SO(4). To elucidate the mechanism of the process, total amounts of chromium and Cr(VI) were analyzed using flame atomic absorption and ultraviolet-visible (UV-vis) spectroscopic techniques, respectively. The Langmuir and Dubinin-Radushkevich (D-R) isotherms were used to describe the partitioning behavior for the system at different temperatures. Kinetics and thermodynamics of Cr(VI) removal by banana peel were also studied. The influence of diverse ions on the sorption behavior revealed that only Fe(II) ions (of those tested) suppressed the sorption of Cr(VI) ions to some extent. The method was applied for the removal of Cr(VI) from industrial wastewater.

Pseudotetrahedral manganese complexes supported by the anionic tris(phosphino)borate ligand [PhBPiPr3

PubMed Central

Lu, Connie C.; Peters, Jonas C.

2008-01-01

This paper presents aspects of the coordination chemistry of mono- and divalent manganese complexes supported by the anionic tris(phosphino)borate ligand, [PhBPiPr3] (where [PhBPiPr3] = [PhB(CH2PiPr2)3]−). The Mn(II) halide complexes, [PhBPiPr3]MnCl (1 and [PhBPiPr3]MnI (2), have been characterized by X-ray diffraction, SQUID magnetometry, and EPR spectroscopy. Compound 2 serves as a precursor to a series of Mn azide, alkyl, and amide species: [PhBPiPr3]Mn(N3) (3), [PhBPiPr3]Mn(CH2Ph) (4), [PhBPiPr3]Mn(Me) (5), [PhBPiPr3]Mn(NH(2,6-iPr2-C6H3)) (6), [PhBPiPr3]Mn(dbabh) (7), and [PhBPiPr3]Mn(1-Ph(isoindolate)) (8). The complexes 2 – 8 feature a divalent-metal center and are pseudotetrahedral. They collectively represent an uncommon structural motif for low-coordinate, polyphosphine-supported Mn complexes. Two Mn(I) species have also been prepared. These include the Tl-Mn adduct, [PhBPiPr3]Tl-MnBr(CO)4 (9), and the octahedral complex [PhBPiPr3]Mn(CNtBu)3 (10). Some of our initial synthetic efforts to generate [PhBPiPr3]Mn≡Nx species are briefly described, as are DFT studies that probe the electronic viability of these types of multiply bonded target structures. PMID:17029370

Investigation of sorption/desorption equilibria of heavy metal ions on/from quartz using rhamnolipid biosurfactant.

PubMed

Aşçi, Yeliz; Nurbaş, Macid; Sağ Açikel, Yeşim

2010-01-01

In the present study, the sorption characteristics of Cd(II) and Zn(II) ions on quartz, a representative soil-component, and the desorption of these metal ions from quartz using rhamnolipid biosurfactant were investigated. In the first part of the studies, the effects of initial metal ion concentration and pH on sorption of Cd(II) and Zn(II) ions by a fixed amount of quartz (1.5g) were studied in laboratory batch mode. The equilibrium sorption capacity for Cd(II) and Zn(II) ions was measured and the best correlation between experimental and model predicted equilibrium uptake was obtained using the Freundlich model. Although investigations on the desorption of heavy metal ions from the main soil-components are crucial to better understand the mobility and bioavailability of metals in the environment, studies on the description of desorption equilibrium were performed rarely. In the second part, the desorption of Cd(II) and Zn(II) from quartz using rhamnolipid biosurfactant was investigated as a function of pH, rhamnolipid concentration, and the amounts of sorbed Cd(II) and Zn(II) ions by quartz. The Freundlich model was also well fitted to the obtained desorption isotherms. Several indexes were calculated based on the differences of the quantity of Cd-Zn sorbed and desorbed. A desorption hysteresis (irreversibility) index based on the Freundlich exponent, concentration-dependent metal distribution coefficients, and the irreversibility index based on the metal distribution coefficient were used to quantify hysteretic behavior observed in the systems. 2009 Elsevier Ltd. All rights reserved.

Removal of cadmium ions from wastewater using innovative electronic waste-derived material.

PubMed

Xu, Meng; Hadi, Pejman; Chen, Guohua; McKay, Gordon

2014-05-30

Cadmium is a highly toxic heavy metal even at a trace level. In this study, a novel material derived from waste PCBs has been applied as an adsorbent to remove cadmium ions from aqueous solutions. The effects of various factors including contact time, initial cadmium ion concentration, pH and adsorbent dosage have been evaluated. The maximum uptake capacity of the newly derived material for cadmium ions has reached 2.1mmol/g at an initial pH 4. This value shows that this material can effectively remove cadmium ions from effluent. The equilibrium isotherm has been analyzed using several isotherm equations and is best described by the Redlich-Peterson model. Furthermore, different commercial adsorbent resins have been studied for comparison purposes. The results further confirm that this activated material is highly competitive with its commercial counterparts. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption and desorption of lead (II) from wastewater by green algae Cladophora fascicularis.

PubMed

Deng, Liping; Su, Yingying; Su, Hua; Wang, Xinting; Zhu, Xiaobin

2007-05-08

Biosorption is an effective method to remove heavy metals from wastewater. In this work, adsorption features of Cladophora fascicularis were investigated as a function of time, initial pH, initial Pb(II) concentrations, temperature and co-existing ions. Kinetics and equilibria were obtained from batch experiments. The biosorption kinetics followed the pseudo-second order model. Adsorption equilibria were well described by the Langmuir and Freundlich isotherm models. The maximum adsorption capacity was 198.5 mg/g at 298K and pH 5.0. The adsorption processes were endothermic and the biosorption heat was 29.6 kJ/mol. Desorption experiments indicated that 0.01 mol/L Na(2)EDTA was an efficient desorbent for the recovery of Pb(II) from biomass. IR spectrum analysis suggested amido or hydroxy, CO and C-O could combine intensively with Pb(II).

Chemodynamics of heavy metals in long-term contaminated soils: metal speciation in soil solution.

PubMed

Kim, Kwon-Rae; Owens, Gary

2009-01-01

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, CU2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%-52%) and Zn2+ (11%-72%) in soil solutions were generally higher than those of Cu2+ (0.2%-30%) and Pb2+ (0.6%-10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (K(p)) and dissolved organic carbon did not show any significant influence on K(p).

Removal of inorganic mercury from aquatic environments by multi-walled carbon nanotubes.

PubMed

Yaghmaeian, Kamyar; Khosravi Mashizi, Reza; Nasseri, Simin; Mahvi, Amir Hossein; Alimohammadi, Mahmood; Nazmara, Shahrokh

2015-01-01

Mercury is considered as a toxic heavy metal in aquatic environments due to accumulation in bodies of living organisms. Exposure to mercury may lead to different toxic effects in humans including damages to kidneys and nervous system. Multi-walled carbon nanotubes (MWCNTs) were selected as sorbent to remove mercury from aqueous solution using batch technique. ICP instrument was used to determine the amount of mercury in solution. Moreover, pH, contact time and initial concentration of mercury were studied to determine the influence of these parameters on the adsorption conditions. Results indicate that the adsorption strongly depended on pH and the best pH for adsorption is about 7. The rate of adsorption process initially was rapid but it was gradually reduced with increasing of contact time and reached the equilibrium after 120 min. In addition, more than 85 % of initial concentration of 0.1 mg/l was removed at 0.5 g/l concentration of sorbent and contact time of 120 min. Meanwhile, the adsorption process followed the pseudo second-order model and the adsorption isotherms could be described by both the Freundlich and the Langmuir models. This study showed that MWCNTs can effectively remove inorganic mercury from aqueous solutions as adsorbent.

The transport behavior of As, Cu, Pb, and Zn during electrokinetic remediation of a contaminated soil using electrolyte conditioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jung-Seok; Kwon, Man Jae; Choi, Jaeyoung

2014-12-01

Electrokinetic remediation (also known as electrokinetics) is a promising technology for removing metals from fine-grained soils. However, few studies have been conducted regarding the transport behavior of multi-metals during electrokinetics. We investigated the transport of As, Cu, Pb, and Zn from soils during electrokinetics, the metal fractionation before and after electrokinetics, the relationships between metal transport and fractionation, and the effects of electrolyte conditioning. The main transport mechanisms of the metals were electroosmosis and electromigration during the first two weeks and electromigration during the following weeks. The direction of electroosmotic flow was from the anode to the cathode, and themore » metals in the dissolved and reducible-oxides fractions were transported to the anode or cathode by electromigration according to the chemical speciation of the metal ions in the pore water. Moreover, a portion of the metals that were initially in the residual fraction transitioned to the reducible and soluble fractions during electrokinetic treatment. However, this alteration was slow and resulted in decreasing metal removal rates as the electrokinetic treatment progressed. In addition, the use of NaOH, H3PO4, and Na2SO4 as electrolytes resulted in conditions that favored the precipitation of metal hydroxides, phosphates, and sulfates in the soil. These results demonstrated that metal removal was affected by the initial metal fractionation, metal speciation in the pore solution, and the physical–chemical parameters of the electrolytes, such as pH and electrolyte composition. Therefore, the treatment time, use of chemicals, and energy consumption could be reduced by optimizing pretreatment and by choosing appropriate electrolytes for the target metals.« less

Denitrification potential in stream sediments impacted by acid mine drainage: Effects of pH, various electron donors, and iron

USGS Publications Warehouse

Baeseman, J.L.; Smith, R.L.; Silverstein, J.

2006-01-01

Acid mine drainage (AMD) contaminates thousands of kilometers of stream in the western United States. At the same time, nitrogen loading to many mountain watersheds is increasing because of atmospheric deposition of nitrate and increased human use. Relatively little is known about nitrogen cycling in acidic, heavy-metal-laden streams; however, it has been reported that one key process, denitrification, is inhibited under low pH conditions. The objective of this research was to investigate the capacity for denitrification in acidified streams. Denitrification potential was assessed in sediments from several Colorado AMD-impacted streams, ranging from pH 2.60 to 4.54, using microcosm incubations with fresh sediment. Added nitrate was immediately reduced to nitrogen gas without a lag period, indicating that denitrification enzymes were expressed and functional in these systems. First-order denitrification potential rate constants varied from 0.046 to 2.964 day-1. The pH of the microcosm water increased between 0.23 and 1.49 pH units during denitrification. Additional microcosm studies were conducted to examine the effects of initial pH, various electron donors, and iron (added as ferrous and ferric iron). Decreasing initial pH decreased denitrification; however, increasing pH had little effect on denitrification rates. The addition of ferric and ferrous iron decreased observed denitrification potential rate constants. The addition of glucose and natural organic matter stimulated denitrification potential. The addition of hydrogen had little effect, however, and denitrification activity in the microcosms decreased after acetate addition. These results suggest that denitrification can occur in AMD streams, and if stimulated within the environment, denitrification might reduce acidity. ?? Springer Science+Business Media, Inc. 2006.

Lability of Cd, Cu, and Zn in polluted soils treated with lime, beringite, and red mud and identification of a non-labile colloidal fraction of metals using istopic techniques.

PubMed

Lombi, Enzo; Hamon, Rebecca E; McGrath, Steve P; McLaughlin, Mike J

2003-03-01

The use of soil amendments has been proposed as a low input alternative for the remediation of metal polluted soils. However, little information is available concerning the stability, and therefore the longevity, of the remediation treatments when important soil parameters change. In this paper we investigate the effect of pH changes on the lability of heavy metals in soils treated with lime, beringite, and red mud using a modified isotopic dilution technique in combination with a stepwise acidification procedure. Significant amounts of nonlabile (fixed) Cu and Zn were found to be associated with colloids <0.2 microm in the solution phase. The results obtained indicated that the mobility of fixed colloidal metals is significant and increases with soil pH. This must be considered because most of the soil amendments are alkaline and increase soil pH. All the soil amendments significantly decreased the lability of Cd, Zn, and Cu in the soils as a whole. However, when the soils were re-acidified, the labile pool of metals increased sharply and in the case of lime and beringite, the lability of the metals was similar, at equal pH, to the untreated soil. In contrast the lability of metals in the red mud treated soils was always smaller than that in the untreated soils across the range of pH values tested. These results suggest that the mechanism of action of lime and beringite is similar and probably related to increased metal adsorption and precipitation of metal hydroxides and carbonates at high pH. In the case of red mud, a combination of pH dependent and independent mechanisms (possibly solid-phase diffusion or migration into micropores) may be responsible for the metal fixation observed.

Removal of trace metal contaminants from potable water by electrocoagulation

PubMed Central

Heffron, Joe; Marhefke, Matt; Mayer, Brooke K.

2016-01-01

This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency. PMID:27324564

Prediction of phycoremediation of As(III) and As(V) from synthetic wastewater by Chlorella pyrenoidosa using artificial neural network

NASA Astrophysics Data System (ADS)

Podder, M. S.; Majumder, C. B.

2017-11-01

An artificial neural network (ANN) model was developed to predict the phycoremediation efficiency of Chlorella pyrenoidosa for the removal of both As(III) and As(V) from synthetic wastewater based on 49 data-sets obtained from experimental study and increased the data using CSCF technique. The data were divided into training (60%) validation (20%) and testing (20%) sets. The data collected was used for training a three-layer feed-forward back propagation (BP) learning algorithm having 4-5-1 architecture. The model used tangent sigmoid transfer function at input to hidden layer ( tansing) while a linear transfer function ( purelin) was used at output layer. Comparison between experimental results and model results gave a high correlation coefficient (R allANN 2 equal to 0.99987 for both ions and exhibited that the model was able to predict the phycoremediation of As(III) and As(V) from wastewater. Experimental parameters influencing phycoremediation process like pH, inoculum size, contact time and initial arsenic concentration [either As(III) or As(V)] were investigated. A contact time of 168 h was mainly required for achieving equilibrium at pH 9.0 with an inoculum size of 10% (v/v). At optimum conditions, metal ion uptake enhanced with increasing initial metal ion concentration.

Remediation of an acidic mine spoil: Miscanthus biochar and lime amendment affects metal availability, plant growth, and soil enzyme activity.

PubMed

Novak, Jeffrey M; Ippolito, James A; Ducey, Thomas F; Watts, Donald W; Spokas, Kurt A; Trippe, Kristin M; Sigua, Gilbert C; Johnson, Mark G

2018-08-01

Biochar may be a tool for mine spoil remediation; however, its mechanisms for achieving this goal remain unclear. In this study, Miscanthus (Miscanthus giganteus) biochar was evaluated for its ability to reclaim acidic mine spoils (pH < 3) through reducing metal availability, improving soil microbial enzymatic activity, and initial growth of grass seedlings. Biochar was applied at 0, 1, 2.5 and 5% (w/w) along with lime/no lime and fertilizer additions. Blue Wildrye (Elymus glaucus cv. 'Elkton') was planted and later the shoots and roots were collected and metal concentrations determined. Afterwards, each pot was leached with deionized water, and the leachate analyzed for pH, electrical conductivity (EC), dissolved organic carbon (DOC) and soluble metal concentrations. After drying, the spoil was extracted with 0.01 M CaCl 2 and Mehlich 3 (M3) to determine extractable Al, Cu, and Zn concentrations. Additionally, microbial activity was measured using a fluorescent β-glucosidase and N-acetyl-β-d-glucosaminidase assay. Spoil treated with lime and biochar had significantly greater pH and EC values. Significantly greater β-glucosidase activity occurred only in the 5% biochar plus lime treatment, while N-acetyl-β-d-glucosaminidase activities were not altered. Metal concentrations in rye shoot and roots were mixed. Lime additions significantly reduced extractable metal concentrations. Increasing biochar rates alone significantly reduced leachate DOC concentrations, and subsequently reduced leachable metal concentrations. Surprisingly, miscanthus biochar, by itself, was limited at mitigation, but when combined with lime, the combination was capable of further reducing extractable metal concentrations and improving β-glucosidase enzyme activity. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

A novel approach for rapidly and cost-effectively assessing toxicity of toxic metals in acidic water using an acidophilic iron-oxidizing biosensor.

PubMed

Yang, Shih-Hung; Cheng, Kuo-Chih; Liao, Vivian Hsiu-Chuan

2017-11-01

Contamination by heavy metals and metalloids is a serious environmental and health concern. Acidic wastewaters are often associated with toxic metals which may enter and spread into agricultural soils. Several biological assays have been developed to detect toxic metals; however, most of them can only detect toxic metals in a neutral pH, not in an acidic environment. In this study, an acidophilic iron-oxidizing bacterium (IOB) Strain Y10 was isolated, characterized, and used to detect toxic metals toxicity in acidic water at pH 2.5. The colorimetric acidophilic IOB biosensor was based on the inhibition of the iron oxidizing ability of Strain Y10, an acidophilic iron-oxidizing bacterium, by metals toxicity. Our results showed that Strain Y10 is acidophilic iron-oxidizing bacterium. Thiobacillus caldus medium (TCM) (pH 2.5) supplied with both S 4 O 6 2- and glucose was the optimum growth medium for Strain Y10. The optimum temperature and pH for the growth of Strain Y10 was 45 °C and pH 2.5, respectively. Our study demonstrates that the color-based acidophilic IOB biosensor can be semi-quantitatively observed by eye or quantitatively measured by spectrometer to detect toxicity from multiple toxic metals at pH 2.5 within 45 min. Our study shows that monitoring toxic metals in acidic water is possible by using the acidophilic IOB biosensor. Our study thus provides a novel approach for rapid and cost-effective detection of toxic metals in acidic conditions that can otherwise compromise current methods of chemical analysis. This method also allows for increased efficiency when screening large numbers of environmental samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Divalent metals and pH alter raltegravir disposition in vitro.

PubMed

Moss, Darren M; Siccardi, Marco; Murphy, Matthew; Piperakis, Michael M; Khoo, Saye H; Back, David J; Owen, Andrew

2012-06-01

Raltegravir shows marked pharmacokinetic variability in patients, with gastrointestinal pH and divalent-metal binding being potential factors. We investigated raltegravir solubility, lipophilicity, pK(a), and permeativity in vitro to elucidate known interactions with omeprazole, antacids, and food, all of which increase gastric pH. Solubility of raltegravir was determined at pH 1 to 8. Lipophilicity of raltegravir was determined using octanol-water partition. Raltegravir pK(a) was determined using UV spectroscopy. The effects of pH, metal salts, and omeprazole on the cellular permeativity of raltegravir were determined using Caco-2 monolayers. Cellular accumulation studies were used to determine the effect of interplay between pH and ABCB1 transport on raltegravir accumulation. Samples were analyzed using liquid chromatography-tandem mass spectroscopy (LC-MS/MS) or scintillation counting. Raltegravir at 10 mM was partly insoluble at pH 6.6 and below. Raltegravir lipophilicity was pH dependent and was reduced as pH was increased from 5 to 9. The pK(a) of raltegravir was 6.7. Raltegravir cellular permeativity was heavily influenced by changes in extracellular pH, where apical-to-basolateral permeativity was reduced 9-fold (P < 0.05) when apical pH was increased from 5 to 8.5. Raltegravir cellular permeativity was also reduced in the presence of magnesium and calcium. Omeprazole did not alter raltegravir cellular permeativity. Cellular accumulation of raltegravir was increased independently by inhibiting ABCB1 and by lowering extracellular pH from pH 8 to 5. Gastrointestinal pH and polyvalent metals can potentially alter the pharmacokinetic properties of raltegravir, and these data provide an explanation for the variability in raltegravir exposure in patients. The evaluation of how divalent-metal-containing products, such as multivitamins, that do not affect gastric pH alter raltegravir pharmacokinetics in patients is now justified.

Divalent Metals and pH Alter Raltegravir Disposition In Vitro

PubMed Central

Moss, Darren M.; Siccardi, Marco; Murphy, Matthew; Piperakis, Michael M.; Khoo, Saye H.; Back, David J.

2012-01-01

Raltegravir shows marked pharmacokinetic variability in patients, with gastrointestinal pH and divalent-metal binding being potential factors. We investigated raltegravir solubility, lipophilicity, pKa, and permeativity in vitro to elucidate known interactions with omeprazole, antacids, and food, all of which increase gastric pH. Solubility of raltegravir was determined at pH 1 to 8. Lipophilicity of raltegravir was determined using octanol-water partition. Raltegravir pKa was determined using UV spectroscopy. The effects of pH, metal salts, and omeprazole on the cellular permeativity of raltegravir were determined using Caco-2 monolayers. Cellular accumulation studies were used to determine the effect of interplay between pH and ABCB1 transport on raltegravir accumulation. Samples were analyzed using liquid chromatography-tandem mass spectroscopy (LC-MS/MS) or scintillation counting. Raltegravir at 10 mM was partly insoluble at pH 6.6 and below. Raltegravir lipophilicity was pH dependent and was reduced as pH was increased from 5 to 9. The pKa of raltegravir was 6.7. Raltegravir cellular permeativity was heavily influenced by changes in extracellular pH, where apical-to-basolateral permeativity was reduced 9-fold (P < 0.05) when apical pH was increased from 5 to 8.5. Raltegravir cellular permeativity was also reduced in the presence of magnesium and calcium. Omeprazole did not alter raltegravir cellular permeativity. Cellular accumulation of raltegravir was increased independently by inhibiting ABCB1 and by lowering extracellular pH from pH 8 to 5. Gastrointestinal pH and polyvalent metals can potentially alter the pharmacokinetic properties of raltegravir, and these data provide an explanation for the variability in raltegravir exposure in patients. The evaluation of how divalent-metal-containing products, such as multivitamins, that do not affect gastric pH alter raltegravir pharmacokinetics in patients is now justified. PMID:22450971

Metals sorption from aqueous solutions by Kluyveromyces marxianus: process optimization, equilibrium modeling and chemical characterization.

PubMed

Pal, Rama; Tewari, Saumyata; Rai, Jai P N

2009-10-01

The dead Kluyveromyces marxianus biomass, a fermentation industry waste, was used to explore its sorption potential for lead, mercury, arsenic, cobalt, and cadmium as a function of pH, biosorbent dosage, contact time, agitation speed, and initial metal concentration. The equilibrium data fitted the Langmuir model better for cobalt and cadmium, but Freundlich isotherm for all metals tested. At equilibrium, the maximum uptake capacity (Qmax) was highest for lead followed by mercury, arsenic, cobalt, and cadmium. The RL values ranged between 0-1, indicating favorable sorption of all test metals by the biosorbent. The maximum Kf value of Pb showed its efficient removal from the solution. However, multi-metal analysis depicted that sorption of all metals decreased except Pb. The potentiometric titration of biosorbent revealed the presence of functional groups viz. amines, carboxylic acids, phosphates, and sulfhydryl group involved in heavy metal sorption. The extent of contribution of functional groups and lipids to biosorption was in the order: carboxylic>lipids>amines>phosphates. Blocking of sulfhydryl group did not have any significant effect on metal sorption.

Flow microcapillary plasma mass spectrometry-based investigation of new Al-Cr-Fe complex metallic alloy passivation.

PubMed

Ott, N; Beni, A; Ulrich, A; Ludwig, C; Schmutz, P

2014-03-01

Al-Cr-Fe complex metallic alloys are new intermetallic phases with low surface energy, low friction, and high corrosion resistance down to very low pH values (0-2). Flow microcapillary plasma mass spectrometry under potentiostatic control was used to characterize the dynamic aspect of passivation of an Al-Cr-Fe gamma phase in acidic electrolytes, allowing a better insight on the parameters inducing chemical stability at the oxyhydroxide-solution interface. In sulfuric acid pH 0, low element dissolution rates (in the µg cm(-2) range after 60 min) evidenced the passive state of the Al-Cr-Fe gamma phase with a preferential over-stoichiometric dissolution of Al and Fe cations. Longer air-aging was found to be beneficial for stabilizing the passive film. In chloride-containing electrolytes, ten times higher Al dissolution rates were detected at open-circuit potential (OCP), indicating that the spontaneously formed passive film becomes unstable. However, electrochemical polarization at low passive potentials induces electrical field generated oxide film modification, increasing chemical stability at the oxyhydroxide-solution interface. In the high potential passive region, localized attack is initiated with subsequent active metal dissolution. © 2013 Published by Elsevier B.V.

Hexavalent chromium removal by using synthesis of polyaniline and polyvinyl alcohol.

PubMed

Riahi Samani, Majid; Ebrahimbabaie, Parisa; Vafaei Molamahmood, Hamed

2016-11-01

Over the past few years, heavy metals have been proved to be one of the most important contaminants in industrial wastewater. Chromium is one of these heavy metals, which is being utilized in several industries such as textile, finishing and leather industries. Since hexavalent chromium is highly toxic to human health, removal of it from the wastewater is essential for human safety. One of the techniques for removing chromium (VI) is the use of different adsorbents such as polyaniline. In this study, composites of polyaniline (PANi) were synthesized with various amounts of polyvinyl alcohol (PVA). The results showed that PANi/PVA removed around 76% of chromium at a pH of 6.5; the PVA has altered the morphology of the composites and increased the removal efficiency. Additionally, synthesis of 20 mg/L of PVA by PANi composite showed the best removal efficiency, and the optimal stirring time was calculated as 30 minutes. Moreover, the chromium removal efficiency was increased by decreasing the pH, initial chromium concentration and increasing stirring time.

Isolation, identification, and culture optimization of a novel glycinonitrile-hydrolyzing fungus-Fusarium oxysporum H3.

PubMed

Gong, Jin-Song; Lu, Zhen-Ming; Shi, Jing-Song; Dou, Wen-Fang; Xu, Hong-Yu; Zhou, Zhe-Min; Xu, Zheng-Hong

2011-10-01

Microbial transformation of glycinonitrile into glycine by nitrile hydrolase is of considerable interest to green chemistry. A novel fungus with high nitrile hydrolase was newly isolated from soil samples and identified as Fusarium oxysporum H3 through 18S ribosomal DNA, 28S ribosomal DNA, and the internal transcribed spacer sequence analysis, together with morphology characteristics. After primary optimization of culture conditions including pH, temperature, carbon/nitrogen sources, inducers, and metal ions, the enzyme activity was greatly increased from 326 to 4,313 U/L. The preferred carbon/nitrogen sources, inducer, and metal ions were glucose and yeast extract, caprolactam, and Cu(2+), Mn(2+), and Fe(2+), respectively. The maximum enzyme formation was obtained when F. oxysporum H3 was cultivated at 30 °C for 54 h with the initial pH of 7.2. There is scanty report about the optimization of nitrile hydrolase production from nitrile-converting fungus.

Study of Strength Characteristics of Steel Specimens after Selective Laser Melting of Powder Materials 17-4PH, 316L, 321

NASA Astrophysics Data System (ADS)

Zhukov, Anton; Barakhtin, Boris; Kuznetsov, Pavel

By the method of selective laser melting of powder materials nanostructured stainless steels 17-4PH, 316L, 321 were obtained. In all experiments the recorded hardness increase depending on the construction parameters. Obtained relationship of hardness increase with the carbon ratio, which explained by the chemical composition of the metal in the melting zone. It is suggested that the effect of hardness increase is associated with structural changes as to the formation and dissolution of hardening nanophases. Methods of metallography were performed in structural studies. Traces of interlayer segregation were detected inside the grains as turbulent eddies in the bands of different saturation tone caused by the migration of convective (mass transfer) metal atoms. It was visible signs of crystallization through the grain places the image (dendrite crystals). These facts revealed structural features suggest that the adhesion layers of melted powder was initiated by the colder layers and going mechanism epitaxy by coherently oriented groups of atoms from layers of melting.

Kinetics of Cd(ii) adsorption and desorption on ferrihydrite: experiments and modeling.

PubMed

Liang, Yuzhen; Tian, Lei; Lu, Yang; Peng, Lanfang; Wang, Pei; Lin, Jingyi; Cheng, Tao; Dang, Zhi; Shi, Zhenqing

2018-05-15

The kinetics of Cd(ii) adsorption/desorption on ferrihydrite is an important process affecting the fate, transport, and bioavailability of Cd(ii) in the environment, which was rarely systematically studied and understood at quantitative levels. In this work, a combination of stirred-flow kinetic experiments, batch adsorption equilibrium experiments, high-resolution transmission electron microscopy (HR-TEM), and mechanistic kinetic modeling were used to study the kinetic behaviors of Cd(ii) adsorption/desorption on ferrihydrite. HR-TEM images showed the open, loose, and sponge-like structure of ferrihydrite. The batch adsorption equilibrium experiments revealed that higher pH and initial metal concentration increased Cd(ii) adsorption on ferrihydrite. The stirred-flow kinetic results demonstrated the increased adsorption rate and capacity as a result of the increased pH, influent concentration, and ferrihydrite concentration. The mechanistic kinetic model successfully described the kinetic behaviors of Cd(ii) during the adsorption and desorption stages under various chemistry conditions. The model calculations showed that the adsorption rate coefficients varied as a function of solution chemistry, and the relative contributions of the weak and strong ferrihydrite sites for Cd(ii) binding varied with time at different pH and initial metal concentrations. Our model is able to quantitatively assess the contributions of each individual ferrihydrite binding site to the overall Cd(ii) adsorption/desorption kinetics. This study provided insights into the dynamic behavior of Cd(ii) and a predictive modeling tool for Cd(ii) adsorption/desorption kinetics when ferrihydrite is present, which may be helpful for the risk assessment and management of Cd contaminated sites.

Metal-Folded Single-Chain Nanoparticle: Nanoclusters and Self-Assembled Reduction-Responsive Sub-5-nm Discrete Subdomains.

PubMed

Cao, Hui; Cui, Zhigang; Gao, Pan; Ding, Yi; Zhu, Xuechao; Lu, Xinhua; Cai, Yuanli

2017-09-01

Easy access to discrete nanoclusters in metal-folded single-chain nanoparticles (metal-SCNPs) and independent ultrafine sudomains in the assemblies via coordination-driven self-assembly of hydrophilic copolymer containing 9% imidazole groups is reported herein. 1 H NMR, dynamic light scattering, and NMR diffusion-ordered spectroscopy results demonstrate self-assembly into metal-SCNPs (>70% imidazole-units folded) by neutralization in the presence of Cu(II) in water to pH 4.6. Further neutralization induces self-assembly of metal-SCNPs (pH 4.6-5.0) and shrinkage (pH 5.0-5.6), with concurrent restraining residual imidazole motifs and hydrophilic segment, which organized into constant nanoparticles over pH 5.6-7.5. Atomic force microscopy results evidence discrete 1.2 nm nanoclusters and sub-5-nm subdomains in metal-SCNP and assembled nanoparticle. Reduction of metal center using sodium ascorbate induces structural rearrangement to one order lower than the precursor. Enzyme mimic catalysis required media-tunable discrete ultrafine interiors in metal-SCNPs and assemblies have hence been achieved. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of age and rainfall pH on contaminant yields from metal roofs.

PubMed

Wicke, Daniel; Cochrane, Thomas A; O'Sullivan, Aisling D; Cave, Simon; Derksen, Mark

2014-01-01

Metal roofs are recognized for conveying significant metal loads to urban streams through stormwater runoff. Metal concentrations in urban runoff depend on roof types and prevailing weather conditions but the combined effects of roof age and rainfall pH on metal mobilization are not well understood. To investigate these effects on roof runoff, water quality was analysed from galvanized iron and copper roofs following rainfall events and also from simulating runoff using a rainfall simulator on specially constructed roof modules. Zinc and copper yields under different pH regimes were investigated for two roof materials and two different ages. Metal mobilization from older roofs was greater than new roofs with 55-year-old galvanized roof surfaces yielding more Zn, on average increasing by 45% and 30% under a rainfall pH of 4 and 8, respectively. Predominantly dissolved (85-95%) Zn and Cu concentrations in runoff exponentially increased as the rainfall pH decreased. Results also confirmed that copper guttering and downpipes associated with galvanized steel roof systems can substantially increase copper levels in roof runoff. Understanding the dynamics of roof surfaces as a function of weathering and rainfall pH regimes can help developers with making better choices about roof types and materials for stormwater improvement.

Flotation as a remediation technique for heavily polluted dredged material. 1. A feasibility study.

PubMed

Cauwenberg, P; Verdonckt, F; Maes, A

1998-01-19

The flotation behaviour of highly polluted dredged material was investigated at different pH values by mechanical agitated (Denver) flotation. Up to 80% of cadmium, copper, lead and zinc could be concentrated in the froth layer which represented only 30% of the total mass. The maximum specificity for heavy metals, defined as the concentrating factor, was obtained at pH 8-9. The maximum recovery of heavy metals on the other hand was found to be reached at elevated pH values (pH 12). In addition the specificity of the flotation process for the transition metals could be assigned to their presence as metal sulphides in the dredged material. However, the interaction with organic matter is an important factor in determining their flotability. The carbonate fraction was irrelevant for the flotation behaviour of heavy metals.

Environmental effects on the aquatic system and metal discharge to the Mediterranean Sea from a near-neutral zinc-ferrous sulfate mine drainage

USGS Publications Warehouse

Frau, Franco; Medas, Daniela; Da Pelo, Stefania; Wanty, Richard B.; Cidu, Rosa

2015-01-01

After mine closure in the 1980s and subsequent shutdown of the dewatering system, groundwater rebound led to drainage outflow from the Casargiu gallery (Montevecchio mine, SW Sardinia, Italy) beginning in 1997. Mine drainage had pH 6.0 and dissolved concentrations of sulfate (5000 mg/L) and metals (e.g., 1000 mg/L Zn, 230 mg/L Fe, 150 mg/L Mn) much higher than those previously measured in groundwater under dewatering conditions. As compared with the first stages of rebound at Casargiu, a very high contamination level still persists after more than 15 years of flushing. Mine drainage (20–70 L/s; pH 6.0 ± 0.2; Zn-Mg-Ca-SO4 composition) flowed into the Rio Irvi. Abundant precipitation of amorphous Fe(III)-(oxy)hydroxides occurred. Moreover, sulfate-bearing green rust was observed to flocculate in the reach of the Rio Irvi where pH was still circumneutral. Water sampling along this stream for about 6 km almost to its mouth in the Mediterranean Sea showed a pH decrease from 6.0 to 4.0 and a significant removal of Fe (46 %) and As (96 %), while sulfate, Zn, Mn, Co, Ni, and Cd showed small variations downstream. Lead was initially adsorbed onto Fe(III)-(oxy)hydroxides, then desorbed as pH dropped below 5. The estimated amount of dissolved metals discharged into the Mediterranean Sea is significant (e.g., 900 kg/day Zn, 1.4 kg/day Cd, 5 kg/day Ni). In particular, a conservative estimation of the amount of Zn discharged to the sea is about 330 ton/year, which would correspond to 1.4 % of the global annual flux of dissolved Zn from uncontaminated rivers to the oceans.

Manipulation and measurement of pH sensitive metal-ligand binding using electrochemical proton generation and metal detection.

PubMed

Read, Tania L; Joseph, Maxim B; Macpherson, Julie V

2016-01-31

Generator-detector electrodes can be used to both perturb and monitor pH dependant metal-ligand binding equilibria, in situ. In particular, protons generated at the generator locally influence the speciation of metal (Cu(2+)) in the presence of ligand (triethylenetetraamine), with the detector employed to monitor, in real time, free metal (Cu(2+)) concentrations.

Hexavalent Chromate Reductase Activity in Cell Free Extracts of Penicillium sp.

PubMed Central

Arévalo-Rangel, Damaris L.; Cárdenas-González, Juan F.; Martínez-Juárez, Víctor M.; Acosta-Rodríguez, Ismael

2013-01-01

A chromium-resistant fungus isolated from contaminated air with industrial vapors can be used for reducing toxic Cr(VI) to Cr(III). This study analyzes in vitro reduction of hexavalent chromium using cell free extract(s) of the fungus that was characterized based on optimal temperature, pH, use of electron donors, metal ions and initial Cr(VI) concentration in the reaction mixture. This showed the highest activity at 37°C and pH 7.0; there is an increase in Cr(VI) reductase activity with addition of NADH as an electron donor, and it was highly inhibited by Hg2+, Ca2+ and Mg2+, and azide, EDTA, and KCN. PMID:24027493

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

USGS Publications Warehouse

Power, L.E.; Arai, Y.; Sparks, D.L.

2005-01-01

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

Leachate concentrations from water leach and column leach tests on fly ash-stabilized soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bin-Shafique, S.; Benson, C.H.; Edil, T.B.

2006-01-15

Batch water leaching tests (WLTs) and column leaching tests (CLTs) were conducted on coal-combustion fly ashes, soil, and soil-fly ash mixtures to characterize leaching of Cd, Cr, Se, and Ag. The concentrations of these metals were also measured in the field at two sites where soft fine-grained soils were mechanically stabilized with fly ash. Concentrations in leachate from the WLTs on soil-fly ash mixtures are different from those on fly ash alone and cannot be accurately estimated based on linear dilution calculations using concentrations from WLTs on fly ash alone. The concentration varies nonlinearly with fly ash content due tomore » the variation in pH with fly ash content. Leachate concentrations are low when the pH of the leachate or the cation exchange capacity (CEC) of the soil is high. Initial concentrations from CLTs are higher than concentrations from WLTs due to differences in solid-liquid ratio, pH, and solid-liquid contact. However, both exhibit similar trends with fly ash content, leachate pH, and soil properties. Scaling factors can be applied to WLT concentrations (50 for Ag and Cd, 10 for Cr and Se) to estimate initial concentrations for CLTs. Concentrations in leachate collected from the field sites were generally similar or slightly lower than concentrations measured in CLTs on the same materials. Thus, CLTs appear to provide a good indication of conditions that occur in the field provided that the test conditions mimic the field conditions. In addition, initial concentrations in the field can be conservatively estimated from WLT concentrations using the aforementioned scaling factors provided that the pH of the infiltrating water is near neutral.« less

Bio-extraction of precious metals from urban solid waste

NASA Astrophysics Data System (ADS)

Das, Subhabrata; Natarajan, Gayathri; Ting, Yen-Peng

2017-01-01

Reduced product lifecycle and increasing demand for electronic devices have resulted in the generation of huge volumes of electronic waste (e-waste). E-wastes contain high concentrations of toxic heavy metals, which have detrimental effects on health and the environment. However, e-wastes also contain significant concentrations of precious metals such as gold, silver and palladium, which can be a major driving force for recycling of urban waste. Cyanogenic bacteria such as Chromobacterium violaceum generate cyanide as a secondary metabolite which mobilizes gold into solution via a soluble gold-cyanide complex. However, compared to conventional technology for metal recovery, this approach is not effective, owing largely to the low concentration of lixiviants produced by the bacteria. To overcome the challenges of bioleaching of gold from e-waste, several strategies were adopted to enhance gold recovery rates. These included (i) pretreatment of e-waste to remove competing metal ions, (ii) mutation to adapt the bacteria to high pH environment, (iii) metabolic engineering to produce higher cyanide lixiviant, and (iv) spent medium leaching with adjusted initial pH. Compared to 7.1 % recovery by the wild type bacteria, these strategies achieved gold recoveries of 11.3%, 22.5%, 30% and 30% respectively at 0.5% w/v pulp density respectively. Bioleached gold was finally mineralized and precipitated as gold nanoparticles using the bacterium Delftia acidovorans. This study demonstrates the potential for enhancement of biocyanide production and gold recovery from electronic waste through different strategies, and extraction of solid gold from bioleached leachate.

Preparation of metal-resistant immobilized sulfate reducing bacteria beads for acid mine drainage treatment.

PubMed

Zhang, Mingliang; Wang, Haixia; Han, Xuemei

2016-07-01

Novel immobilized sulfate-reducing bacteria (SRB) beads were prepared for the treatment of synthetic acid mine drainage (AMD) containing high concentrations of Fe, Cu, Cd and Zn using up-flow anaerobic packed-bed bioreactor. The tolerance of immobilized SRB beads to heavy metals was significantly enhanced compared with that of suspended SRB. High removal efficiencies of sulfate (61-88%) and heavy metals (>99.9%) as well as slightly alkaline effluent pH (7.3-7.8) were achieved when the bioreactor was fed with acidic influent (pH 2.7) containing high concentrations of multiple metals (Fe 469 mg/L, Cu 88 mg/L, Cd 92 mg/L and Zn 128 mg/L), which showed that the bioreactor filled with immobilized SRB beads had tolerance to AMD containing high concentrations of heavy metals. Partially decomposed maize straw was a carbon source and stabilizing agent in the initial phase of bioreactor operation but later had to be supplemented by a soluble carbon source such as sodium lactate. The microbial community in the bioreactor was characterized by denaturing gradient gel electrophoresis (DGGE) and sequencing of partial 16S rDNA genes. Synergistic interaction between SRB (Desulfovibrio desulfuricans) and co-existing fermentative bacteria could be the key factor for the utilization of complex organic substrate (maize straw) as carbon and nutrients source for sulfate reduction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanisms governing the leaching of soil metals as a result of disposal of olive mill wastewater on agricultural soils.

PubMed

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2018-07-15

Olive mill wastewater (OMWW) is an acidic, saline, and organic matter-rich aqueous byproduct of olive oil production that is usually disposed of by spreading on agricultural soils. This study tested whether spreading OMWW can release indigenous soil metals (Fe, Mn, Cu and Zn) through pH, redox, and DOM complexation-related mechanisms, using three agricultural soils having different textures and chemical properties, and controlled pH and redox conditions (pH5.6 or 8.4; ORP from -200 to +250mV). Comparison treatments included a solution having the same salt content and composition as OMWW but lacking OM, and deionized water (DW). In all three soils and under all pH and redox conditions, the model salt solution and DW treatments solubilized considerably fewer metal cations than did OMWW. Overall, the primary factor in metals release from the soils by OMWW was the DOM fraction. pH, redox and soil type played secondary but important roles in solubilization of the various metals. pH had a major impact on Mn leaching but no impact on Fe and Cu leaching. Conversely, redox did not affect Mn leaching, but lower redox conditions contributed to elevated release of both Fe and Cu. For the most part, released metals were sourced from water soluble, exchangeable, easily reducible, and moderately reducible soil metals pools. Fe, Mn and Cu released from the soils by OMWW featured mainly as metal-organic complexes, and OMWW generally caused Zn precipitation in the soils. Soils rich in clay and organic matter under reduced pH and low redox conditions released substantially more metal cations than did a sand-rich soil. Spreading OMWW may result in sequestration of essential micronutrients like Zn, and increased availability of other micronutrients such as Fe, Mn and Cu. Copyright © 2018 Elsevier B.V. All rights reserved.

Effects of Siderophores on Metal Adsorption to Kaolinite

NASA Astrophysics Data System (ADS)

Hepinstall, S. E.; Maurice, P. A.; Miller, M. J.

2003-12-01

Siderophores are metal-complexing ligands with high affinities for Fe(III), produced by many microorganisms in Fe-deficient environments. Siderophores can also form strong complexes with other metals such as Pb and Cd; hence, siderophores may play an important role in controlling metal mobility in porous media. This study compared the effects of siderophores desferrioxamine-B (DFO-B), desferrioxamine-D (DFO-D1), desferrioxamine-E (DFO-E), as well as siderophore-like ligand acetohydroxamic acid (aHA) on Pb and Cd adsorption to kaolinite (KGa-1b) at pH 4.5 to 9, in 0.1 M NaClO4, at 22 \\deg C, in the dark. At pH > 6.5 all of the siderophores plus aHA, inhibited Pb adsorption, with inhibition increasing in the order aHA < DFO-D1 < DFO-B < DFO-E. At lower pH, all four ligands slightly enhanced Pb adsorption. These ligands also inhibited Cd adsorption at high pH, but had little or no effect at low pH. These results suggest that siderophore effects on metal mobility through porous media are likely to be complex and variable with pH.

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste

USGS Publications Warehouse

Al-Abed, S. R.; Hageman, P.L.; Jegadeesan, G.; Madhavan, N.; Allen, D.

2006-01-01

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (Eh), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the Eh-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Diel cycling of zinc in a stream impacted by acid rock drainage: Initial results from a new in situ Zn analyzer

USGS Publications Warehouse

Chapin, T.P.; Nimick, D.A.; Gammons, C.H.; Wanty, R.B.

2007-01-01

Recent work has demonstrated that many trace metals undergo dramatic diel (24-h) cycles in near neutral pH streams with metal concentrations reproducibly changing up to 500% during the diel period (Nimick et al., 2003). To examine diel zinc cycles in streams affected by acid rock drainage, we have developed a novel instrument, the Zn-DigiScan, to continuously monitor in situ zinc concentrations in near real-time. Initial results from a 3-day deployment at Fisher Creek, Montana have demonstrated the ability of the Zn-DigiScan to record diel Zn cycling at levels below 100 ??g/l. Longer deployments of this instrument could be used to examine the effects of episodic events such as rainstorms and snowmelt pulses on zinc loading in streams affected by acid rock drainage. ?? Springer Science+Business Media B.V. 2006.

The effect of tannins and pH on the corrosion of metals in wood extracts

Treesearch

Samuel Zelinka; D.S. Stone

2011-01-01

Tannins and pH are often cited as factors that affect the corrosiveness of wood yet there are few data to confirm these statements. The purpose of this paper is to systematically investigate the effect of tannins and pH on corrosion of metals in wood. Four wood species known to vary in both their pH and extractives were chosen and extracted with water. The pH, tannin...

Electro-oxidation and characterization of nickel foam electrode for removing boron.

PubMed

Kartikaningsih, Danis; Huang, Yao-Hui; Shih, Yu-Jen

2017-01-01

The electrocoagulation (EC) using metallic Ni foam as electrodes was studied for the removal of boron from solution. The electrolytic parameters were pH (4-12), current density (0.6-2.5 mA cm -2 ), and initial concentration of boron (10-100 mg L -1 ). Experimental results revealed that removal efficiency was maximized at pH 8-9, and decreased as the pH increased beyond that range. At particular onset potentials (0.5-0.8 V vs. Hg/HgO), the micro-granular nickel oxide that was created on the surface of the nickel metal substrate depended on pH, as determined by cyclic voltammetry. Most of the crystallites of the precipitates comprised a mixed phase of β-Ni(OH) 2 , a theophrastite phase, and NiOOH, as revealed by XRD and SEM analyses. A current density of 1.25 mA cm -2 was effective in the EC of boron, and increasing the concentration of boric acid from 10 to 100 mg L -1 did not greatly impair removal efficiency. A kinetic investigation revealed that the reaction followed a pseudo-second order rate model. The optimal conditions under which 99.2% of boron was removed from treated wastewater with 10 mg L -1 -B, leaving less than 0.1 mg L -1 -B in the electrolyte, were pH 8 and 1.25 mA cm -2 for 120 min. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of a fluorescent chelating ligand for scandium ion having a Schiff base moiety

NASA Astrophysics Data System (ADS)

Yamada, Hiroshi; Kojo, Masahito; Nakahara, Tomomi; Murakami, Kumi; Kakima, Takashi; Ichiba, Hideaki; Yajima, Takehiko; Fukushima, Takeshi

2012-05-01

A fluorescent ligand, 1-(2-hydroxy-3-methoxybenzaldehyde)-4-aminosalicylhydrazone (HMB-ASH), was newly designed and synthesized, and its fluorescence characteristics for metal ions were investigated in the pH range 3.0-10.5 (at a difference of 0.5 for each metal). After testing 31 different metal ions, it was found that HMB-ASH was able to emit fluorescence intensely at 512 nm with an excitation wavelength of 353 nm in the presence of Sc3+, one of the rare earth metals, at pH values around 3.5 and 8.0. The other metal ions hardly showed fluorescence with HMB-ASH. The fluorescence was more intense at pH 8.0, and the detection limit of Sc3+ in a buffer solution (pH 8.0) was approximately 18.8 nmol L-1 (0.85 ppb).

Enhanced biosorption of transition metals by living Chlorella vulgaris immobilized in Ca-alginate beads.

PubMed

Ahmad, Ashfaq; Bhat, A H; Buang, Azizul

2018-02-01

In this study freely suspended and Ca-alginate immobilized C. vulgaris cells were used for the biosorption of Fe(II), Mn(II), and Zn(II) ions, from the aqueous solution. Experimental data showed that biosorption capacity of algal cells was strongly dependent on the operational condition such as pH, initial metal ions concentration, dosages, contact time and temperature. The maximum biosorption of Fe(II) 43.43, Mn(II) 40.98 and Zn(II) 37.43 mg/g was achieved with Ca-alginate immobilized algal cells at optimum pH of 6.0, algal cells dosage 0.6 g/L, and contact time of 450 min at room temperature. The biosorption efficiency of freely suspended and immobilized C. vulgaris cells for heavy metals removal from the industrial wastewater was validated. Modeling of biosorption kinetics showed good agreements with pseudo-second-order. Langmuir and D-R isotherm models exhibited the best fit of experimental data. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) revealed that the biosorption of considered metal ions was feasible, spontaneous and exothermic at 25-45°C. The SEM showed porous morphology which greatly helps in the biosorption of heavy metals. The Fourier transform infrared spectrophotometer (FTIR) and X-rays Photon Spectroscopy (XPS) data spectra indicated that the functional groups predominately involved in the biosorption were C-N, -OH, COO-, -CH, C=C, C=S and -C-. These results shows that immobilized algal cells in alginate beads could potentially enhance the biosorption of considered metal ions than freely suspended cells. Furthermore, the biosorbent has significantly removed heavy metals from industrial wastewater at the optimized condition.

Characterization of potassium hydroxide (KOH) modified hydrochars from different feedstocks for enhanced removal of heavy metals from water.

PubMed

Sun, Kejing; Tang, Jingchun; Gong, Yanyan; Zhang, Hairong

2015-11-01

Hydrochars produced from different feedstocks (sawdust, wheat straw, and corn stalk) via hydrothermal carbonization (HTC) and KOH modification were used as alternative adsorbents for aqueous heavy metals remediation. The chemical and physical properties of the hydrochars and KOH-treated hydrochars were characterized, and the ability of hydrochars for removal of heavy metals from aqueous solutions as a function of reaction time, pH, and initial contaminant concentration was tested. The results showed that KOH modification of hydrochars might have increased the aromatic and oxygen-containing functional groups, such as carboxyl groups, resulting in about 2-3 times increase of cadmium sorption capacity (30.40-40.78 mg/g) compared to that of unmodified hydrochars (13.92-14.52 mg/g). The sorption ability among different feedstocks after modification was as the following: sawdust > wheat straw > corn stack. Cadmium sorption kinetics on modified hydrochars could be interpreted with a pseudo-second order, and sorption isotherm was simulated with Langmuir adsorption model. High cadmium uptake on modified hydrochars was observed over the pH range of 4.0-8.0, while for other heavy metals (Pb(2+), Cu(2+), and Zn(2+)) the range was 4.0-6.0. In a multi-metal system, the sorption capacity of heavy metals by modified hydrochars was also higher than that by unmodified ones and followed the order of Pb(II) > Cu(II) > Cd(II) > Zn(II). The results suggest that KOH-modified hydrochars can be used as a low cost, environmental-friendly, and effective adsorbent for heavy metal removal from aqueous solutions.

Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0

USGS Publications Warehouse

Stanton, M.R.; Gemery-Hill, P. A.; Shanks, Wayne C.; Taylor, C.D.

2008-01-01

High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).

Investigation of Zn2+ and Cd2+ Adsorption Performanceby Different Weathering Basalts

NASA Astrophysics Data System (ADS)

Xue, Q.; Shuo, Q.; Chen, H.

2016-12-01

Geological barriers play an important role in preventing pollution of groundwater. Basalts are common geological media; however, there have not been any studies that report the effect of basalt type on the metal ion adsorption performance. In this study, we explored the metal ion (Zn2+ and Cd2+) adsorption ability of two kinds of weathering basalts: the origin weathering basalt (WB) and the eluvial deposit (ED), both of which were derived from same basaltic formation. Characteristics of the sediments were examined by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Barrett-Joyner-Halenda (BJH) measurement and the rapid potentiometric titration (RPT) method. Batch experiments were performed to evaluate the Zn2+ and Cd2+ adsorption performance of WB and ED and how adsorption was affected by contact time, initial metal ion concentration, pH and ionic strength. Despite WB and ED having similar chemical compositions, WB exhibited better adsorption than ED likely due to the fact that WB was rougher and had more small-sized spherical structures and stronger electrostatic forces. The adsorption process fit the Freundlich isotherm model well. The adsorption efficiency decreased with a decrease of pH (from 4 to 2) and with increasing ionic strength. These results suggest that a geological barrier composed of WB media might be able to effectively sequester metallic contaminants to prevent them from reaching groundwater.

Contemplating the feasibility of vermiculate blended chitosan for heavy metal removal from simulated industrial wastewater

NASA Astrophysics Data System (ADS)

Prakash, N.; Soundarrajan, M.; Arungalai Vendan, S.; Sudha, P. N.; Renganathan, N. G.

2017-12-01

Wastewater contaminated by heavy metals pose great challenges as they are non biodegradable, toxic and carcinogenic to the soil and aquifers. Vermiculite blended with chitosan have been used to remove Cr(VI) and Cd(II) from the industrial wastewater. The results indicate that the vermiculite blended with chitosan adsorb Cr(VI) and Cd(II) from industrial waste water. Batch adsorption experiments were performed as a function of pH 5.0 and 5.5 respectively for chromium and cadmium. The adsorption rate was observed to be 72 and 71 % of chromium and cadmium respectively. The initial optimum contact time for Cr(VI) was 300 min with 59.2 % adsorption and 300 min for Cd(II) with 71.5 % adsorption. Whereas, at 4-6 there is saturation, increasing the solid to liquid ratio for chitosan biopolymers increases the number of active sites available for adsorption. The optimum pH required for maximum adsorption was found to be 5.0 and 5.5 for chromium and cadmium respectively. The experimental equilibrium adsorption data were fitted using Langmuir and Freundlich equations. It was observed that adsorption kinetics of both the metal ions on vermiculite blended chitosan is well be analyzed with pseudo-second-order model. The negative free energy change of adsorption indicates that the process was spontaneous and vermiculite blended chitosan was a favourable adsorbent for both the metals.

A GIS technology based potential eco-risk assessment of metals in urban soils in Beijing, China.

PubMed

Wang, Meie; Bai, Yanying; Chen, Weiping; Markert, Bernd; Peng, Chi; Ouyang, Zhiyun

2012-02-01

Ecological risks of heavy metals in urban soils were evaluated using Beijing, China as an example. Cadmium, Cu, Zn, Pb, Cr and Ni contents of 233 surface soils sampled by 1 min latitude × 1 min longitude grid were used to identify their spatial distribution patterns and potential emission sources. Throughout the city, longer the duration of urbanization greater was the accumulations of heavy metals especially, Cd, Cu, Pb, and Zn. The soil Zn mainly came from the wears of vehicular tires. Point source emissions of heavy metals were few and far in the downwind south-east quadrant of Beijing. The calculated risk indices showed potential median eco-risks in the ancient central city. No potential high eco-risk due to soil-borne heavy metals was found. The potential medium eco-risk areas in Beijing would expand from the initial 24 to 110 km(2) if soil pH were to reduce by 0.5 units in anticipation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery.

PubMed

Jung, Chang-Hwan; Osako, Masahiro

2009-05-01

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.

Effect of pH and temperature on the uptake of cadmium by Lemna minor L

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chawla, G.; Singh, J.; Viswanathan, P.N.

1991-07-01

Many aquatic macrophytes have the capacity to take up toxic heavy metals from polluted water and accumulate them. Cut leaves and intact plants have been suggested for clearing polluted water bodies of heavy metals. However, uptake of metal ion from water is dependent on concentration, pH, temperature, presence of other substances and functional and morphological status of the biotic species. In an attempt to understand any correlation between metal bioconcentration, pH and temperature, the optimal conditions for the removal of cadmium ions by duckweed, Lemna minor (L.) were studied.

Heavy metal removal from waste waters by ion flotation.

PubMed

Polat, H; Erdogan, D

2007-09-05

Flotation studies were carried out to investigate the removal of heavy metals such as copper (II), zinc (II), chromium (III) and silver (I) from waste waters. Various parameters such as pH, collector and frother concentrations and airflow rate were tested to determine the optimum flotation conditions. Sodium dodecyl sulfate and hexadecyltrimethyl ammonium bromide were used as collectors. Ethanol and methyl isobutyl carbinol (MIBC) were used as frothers. Metal removal reached about 74% under optimum conditions at low pH. At basic pH it became as high as 90%, probably due to the contribution from the flotation of metal precipitates.

Synthesis of 1,4,7-triphenyl-1,4,7-triphosphacyclononane: the first metal-free synthesis of a [9]-aneP(3)R(3) ring.

PubMed

Lowry, Daniel J; Helm, Monte L

2010-06-07

The 1,4,7-triphenyl-1,4,7-triphosphacyclononane ([9]-aneP(3)Ph(3)) macrocycle was synthesized through the reaction of lithium bis(2-phenylphosphidoethyl)phenylphosphine with 1,2-dichloroethane. [9]-aneP(3)Ph(3) was subsequently coordinated to a Mo(0) metal center and isolated as the fac-Mo([9]-aneP(3)Ph(3))(CO)(3) metal complex.

Evaluation of heavy metal leaching from coal ash-versus conventional concrete monoliths and debris.

PubMed

Gwenzi, Willis; Mupatsi, Nyarai M

2016-03-01

Application of coal ash in construction materials is constrained by the potential risk of heavy metal leaching. Limited information is available on the comparative heavy metal leaching from coal ash-versus conventional concrete. The current study compared total and leached heavy metal concentrations in unbound coal ash, cement and sand; and investigated the effect of initial leachant pH on heavy metal leaching from coal-ash versus conventional concrete monoliths and their debris. Total Pb, Mn and Zn in coal ash were lower than or similar to that of other materials, while Cu and Fe showed the opposite trend. Leached concentrations of Zn, Pb, Mn, Cu and Fe in unbound coal ash, its concrete and debris were comparable and in some cases even lower than that for conventional concrete. In all cases, leached concentrations accounted for just <1% of the total concentrations. Log-log plots of concentration and cumulative release of Fe versus time based on tank leaching data showed that leaching was dominated by diffusion. Overall, the risk of Zn, Pb, Mn, Cu and Fe leaching from coal ash and its concrete was minimal and comparable to that of conventional concrete, a finding in contrast to widely held public perceptions and earlier results reported in other regions such as India. In the current study the coal ash, and its concrete and debris had highly alkaline pH indicative of high acid neutralizing and pH buffering capacity, which account for the stabilization of Zn, Pb, Mn, Cu and Fe. Based on the low risk of Zn, Pb, Mn, Cu and Fe leaching from the coal ash imply that such coal ash can be incorporated in construction materials such as concrete without adverse impacts on public and environmental health from these constituents. Copyright © 2015 Elsevier Ltd. All rights reserved.

The influence of ph and waterborne metals on egg fertilization of the blue mussel (Mytilus edulis), the oyster (Crassostrea gigas) and the sea urchin (Paracentrotus lividus).

PubMed

Riba, Inmaculada; Gabrielyan, Bardukh; Khosrovyan, Alla; Luque, Angel; Del Valls, T Angel

2016-07-01

This study evaluated the combined effect of pH and metals on the egg fertilization process of two estuarine species, the blue mussel (Mytilus edulis), the oyster (Crassostrea gigas) and a marine species, the sea urchin (Paracentrotus lividus). The success of egg fertilization was examined after exposure of gametes to sediment extracts of various degrees of contamination at pH 6.0, 6.5, 7.0, 7.5 and 8.0. At the pH levels from 6.5 to 8.0, the egg fertilization of the different species demonstrated different sensitivity to metal and/or acidic exposure. In all species, the results revealed that egg fertilization was almost completely inhibited at pH 6.0. The egg fertilization of the blue mussel M. edulis was the least sensitive to the exposure while that of the sea urchin P. lividus demonstrated a concentration-dependent response to the pH levels from 6.5 to 8.0. The results of this study revealed that acidity increased the concentration of several metal ions (Cr, Ni, Cu, Zn, Cd, and Pb) but reduced its availability to the organisms, probably related to the reactivity of the ions with most non-metals or to the competition among metals and other waterborne constituents.

Metal speciation and potential bioavailability changes during discharge and neutralisation of acidic drainage water.

PubMed

Simpson, Stuart L; Vardanega, Christopher R; Jarolimek, Chad; Jolley, Dianne F; Angel, Brad M; Mosley, Luke M

2014-05-01

The discharge of acid drainage from the farm irrigation areas to the Murray River in South Australia represents a potential risk to water quality. The drainage waters have low pH (2.9-5.7), high acidity (up to 1190 mg L(-1) CaCO3), high dissolved organic carbon (10-40 mg L(-1)), and high dissolved Al, Co, Ni and Zn (up to 55, 1.25, 1.30 and 1.10 mg L(-1), respectively) that represent the greatest concern relative to water quality guidelines (WQGs). To provide information on bioavailability, changes in metal speciation were assessed during mixing experiments using filtration (colloidal metals) and Chelex-lability (free metal ions and weak inorganic metal complexes) methods. Following mixing of drainage and river water, much of the dissolved aluminium and iron precipitated. The concentrations of other metals generally decreased conservatively in proportion to the dilution initially, but longer mixing periods caused increased precipitation or adsorption to particulate phases. Dissolved Co, Mn and Zn were typically 95-100% present in Chelex-labile forms, whereas 40-70% of the dissolved nickel was Chelex-labile and the remaining non-labile fraction of dissolved nickel was associated with fine colloids or complexed by organic ligands that increased with time. Despite the different kinetics of precipitation, adsorption and complexation reactions, the dissolved metal concentrations were generally highly correlated for the pooled data sets, indicating that the major factors controlling the concentrations were similar for each metal (pH, dilution, and time following mixing). For dilutions of the drainage waters of less than 1% with Murray River water, none of the metals should exceed the WQGs. However, the high concentrations of metals associated with fine precipitates within the receiving waters may represent a risk to some aquatic organisms. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Sorption of metals on humic acid

NASA Astrophysics Data System (ADS)

Kerndorff, H.; Schnitzer, M.

1980-11-01

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg≫ Fe≫ Pb≫ CuAl ≫ Ni ≫ CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO 2H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation Y = 100/[1 + exp - (A + BX)], where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.

Characterization of 17-4 PH stainless steel foam for biomedical applications in simulated body fluid and artificial saliva environments.

PubMed

Mutlu, Ilven; Oktay, Enver

2013-04-01

Highly porous 17-4 PH stainless steel foam for biomedical applications was produced by space holder technique. Metal release and weight loss from 17-4 PH stainless steel foams was investigated in simulated body fluid and artificial saliva environments by static immersion tests. Inductively coupled plasma-mass spectrometer was employed to measure the concentrations of various metal ions released from the 17-4 PH stainless steel foams into simulated body fluids and artificial saliva. Effect of immersion time and pH value on metal release and weight loss in simulated body fluid and artificial saliva were determined. Pore morphology, pore size and mechanical properties of the 17-4 PH stainless steel foams were close to human cancellous bone. Copyright © 2012 Elsevier B.V. All rights reserved.

A sulfate-reducing bacterium with unusual growing capacity in moderately acidic conditions.

PubMed

Rampinelli, L R; Azevedo, R D; Teixeira, M C; Guerra-Sá, R; Leão, V A

2008-09-01

The use of sulfate-reducing bacteria (SRB) is a cost-effective route to treat sulfate- contaminated waters and precipitate metals. The isolation and characterization of a SRB strain from an AMD in a Brazilian tropical region site was carried out. With a moderately acidic pH (5.5), the C.1 strain began its growth and with continued growth, modified the pH accordingly. The strain under these conditions reduced sulfate at the same rate as an experiment performed using an initial pH of 7.0. The dsrB gene-based molecular approach was used for the characterization of this strain and its phylogenetic affiliation was similar to genus Desulfovibrio sp. The results show an SRB isolate with unexpected sulfate reducing capacity in moderately acidic conditions, bringing new possibilities for the treatment of AMD, as acid water would be neutralized to a mildly acidic condition.

Utilization of ICP/OES for the determination of trace metal binding to different humic fractions.

PubMed

de la Rosa, G; Peralta-Videa, J R; Gardea-Torresdey, J L

2003-02-28

In this study, the use of inductively coupled plasma/optical emission spectrometry (ICP/OES) to determine multi-metal binding to three biomasses, Sphagnum peat moss, humin and humic acids is reported. All the investigations were performed under part per billion (ppb) concentrations. Batch pH profile experiments were performed using multi-metal solutions of Cd(II), Cu(II), Pb(II), Ni(II), Cr(III) and Cr(VI). The results showed that at pH 2 and 3, the metal affinity of the three biomasses exposed to the multi-metal solution that included Cr(III) presented the following order: Cu(II), Pb(II)>Ni(II)>Cr(III)>Cd(II). On the other hand, when Cr(VI) was in the heavy metal mixture, Sphagnum peat moss and humin showed the following affinity: Cu(II), Pb(II)>Ni(II)>Cr(VI)>Cd(II); however, the affinity of the humic acids was: Cu(II)>Pb(II), Cr(VI)>Ni(II)>Cd(II). The results demonstrated that pH values of 4 and 5 were the most favorable for the heavy metal binding process. At pH 5, all the metals, except for Cr(VI), were bound between 90 and 100% to the three biomasses. However, the binding capacity of humic acids decreased at pH 6 in the presence of Cr(VI). The results showed that the ICP/OES permits the determination of heavy metal binding to organic matter at ppb concentration. These results will be very useful in understanding the role of humic substances in the fate and transport of heavy metals, and thus could provide information to develop new methodologies for the removal of low concentrations of toxic heavy metals from contaminated waters.

Effect of immobilized biosorbents on the heavy metals (Cu2+) biosorption with variations of temperature and initial concentration of waste

NASA Astrophysics Data System (ADS)

Siwi, W. P.; Rinanti, A.; Silalahi, M. D. S.; Hadisoebroto, R.; Fachrul, M. F.

2018-01-01

The aims of research is to studying the efficiency of copper removal by combining immobilized microalgae with optimizations of temperature and initial Copper concentration. The research was conducted in batch culture with temperature variations of 25°C, 30°C, and 35°C, as well as initial Cu2+ concentrations (mg/l) of 3, 5, 10, 15 and 20 using monoculture of S. cerevisiae, Chlorella sp., and mixed culture of them both as immobilized biosorbents. The optimum adsorption of 83.4% obtained in temperature of 30°C with an initial waste concentration of 17.62 mg/l, initial biomass concentration of 200 mg, pH of 4, and 120 minutes detention time by the immobilized mixed culture biosorbent. The cell morphology examined using Scanning Electron Microscope (SEM) has proved that the biosorbent surface was damaged after being in contact with copper (waste), implying that heavy metals (molecules) attach to different functional cell surfaces and change the biosorbent surface. The adsorption process of this research follows Langmuir Isotherm with the R2 value close to 1. The immobilized mixed culture biosorbent is capable of optimally removing copper at temperature of 30°C and initial Cu2+ concentration of 17.62 mg/l.

SrCo1−xTixO3−δ perovskites as excellent catalysts for fast degradation of water contaminants in neutral and alkaline solutions

PubMed Central

Miao, Jie; Sunarso, Jaka; Su, Chao; Zhou, Wei; Wang, Shaobin; Shao, Zongping

2017-01-01

Perovskite-like oxides SrCo1−xTixO3−δ (SCTx, x = 0.1, 0.2, 0.4, 0.6) were used as heterogeneous catalysts to activate peroxymonosulfate (PMS) for phenol degradation under a wide pH range, exhibiting more rapid phenol oxidation than Co3O4 and TiO2. The SCT0.4/PMS system produced a high activity at increased initial pH, achieving optimized performance at pH ≥ 7 in terms of total organic carbon removal, the minimum Co leaching and good catalytic stability. Kinetic studies showed that the phenol oxidation kinetics on SCT0.4/PMS system followed the pseudo-zero order kinetics and the rate on SCT0.4/PMS system decreased with increasing initial phenol concentration, decreased PMS amount, catalyst loading and solution temperature. Quenching tests using ethanol and tert-butyl alcohol demonstrated sulfate and hydroxyl radicals for phenol oxidation. This investigation suggested promising heterogeneous catalysts for organic oxidation with PMS, showing a breakthrough in the barriers of metal leaching, acidic pH, and low efficiency of heterogeneous catalysis. PMID:28281656

Evaluation of the potential of indigenous calcareous shale for neutralization and removal of arsenic and heavy metals from acid mine drainage in the Taxco mining area, Mexico.

PubMed

Romero, F M; Núñez, L; Gutiérrez, M E; Armienta, M A; Ceniceros-Gómez, A E

2011-02-01

In the Taxco mining area, sulfide mineral oxidation from inactive tailings impoundments and abandoned underground mines has produced acid mine drainage (AMD; pH 2.2-2.9) enriched in dissolved concentrations (mg l⁻¹) sulfate, heavy metals, and arsenic (As): SO₄²⁻ (pH 1470-5454), zinc (Zn; 3.0-859), iron (Fe; pH 5.5-504), copper (Cu; pH 0.7-16.3), cadmium (Cd; pH 0.3-6.7), lead (Pb; pH < 0.05-1.8), and As (pH < 0.002-0.6). Passive-treatment systems using limestone have been widely used to remediate AMD in many parts of the world. In limestone-treatment systems, calcite simultaneously plays the role of neutralizing and precipitating agent. However, the acid-neutralizing potential of limestone decreases when surfaces of the calcite particles become less reactive as they are progressively coated by metal precipitates. This study constitutes first-stage development of passive-treatment systems for treating AMD in the Taxco mine area using indigenous calcareous shale. This geologic material consists of a mixture of calcite, quartz, muscovite, albite, and montmorillonite. Results of batch leaching test indicate that calcareous shale significantly increased the pH (to values of 6.6-7.4) and decreased heavy metal and As concentrations in treated mine leachates. Calcareous shale had maximum removal efficiency (100%) for As, Pb, Cu, and Fe. The most mobile metals ions were Cd and Zn, and their average percentage removal was 87% and 89%, respectively. In this natural system (calcareous shale), calcite provides a source of alkalinity, whereas the surfaces of quartz and aluminosilicate minerals possibly serve as a preferred locus of deposition for metals, resulting in the neutralizing agent (calcite) beings less rapidly coated with the precipitating metals and therefore able to continue its neutralizing function for a longer time.

beta-Citryl-L-glutamate is an endogenous iron chelator that occurs naturally in the developing brain.

PubMed

Hamada-Kanazawa, Michiko; Kouda, Makiko; Odani, Akira; Matsuyama, Kaori; Kanazawa, Kiyoka; Hasegawa, Tatsuya; Narahara, Masanori; Miyake, Masaharu

2010-01-01

The compound beta-citryl-L-glutamate (beta-CG) was initially isolated from developing brains, while it has also been found in high concentrations in testes and eyes. However, its functional roles are unclear. To evaluate its coordination with metal ions, we performed pH titration experiments. The stability constant, logbeta(pqr) for M(p)(beta-CG)(q)H(r) was calculated from pH titration data, which showed that beta-CG forms relatively strong complexes with Fe(III), Cu(II), Fe(II) and Zn(II). beta-CG was also found able to solubilize Fe more effectively from Fe(OH)(2) than from Fe(OH)(3). Therefore, we examined the effects of beta-CG on Fe-dependent reactive oxygen species (ROS)-generating systems, as well as the potential ROS-scavenging activities of beta-CG and metal ion-(beta-CG) complexes. beta-CG inhibited the Fe-dependent degradation of deoxyribose and Fe-dependent damage to DNA or plasmid DNA in a dose-dependent manner, whereas it had no effect on Cu-mediated DNA damage. In addition, thermodynamic data showed that beta-CG in a physiological pH solution is an Fe(II) chelator rather than an Fe(III) chelator. Taken together, these findings suggest that beta-CG is an endogenous low molecular weight Fe chelator.

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods.

PubMed

Chiang, Kung-Yuh; Tsai, Chen-Chiu; Wang, Kuen-Sheng

2009-01-01

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag.

PubMed

Xue, Yongjie; Hou, Haobo; Zhu, Shujing

2009-02-15

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

PubMed

Gärtner, Martin; Fischer, Reinald; Langer, Jens; Görls, Helmar; Walther, Dirk; Westerhausen, Matthias

2007-06-11

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

Investigation of simultaneous biosorption of copper(II) and chromium(VI) on dried Chlorella vulgaris from binary metal mixtures: Application of multicomponent adsorption isotherms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aksu, Z.; Acikel, U.; Kutsal, T.

1999-02-01

Although the biosorption of single metal ions to various kinds of microorganisms has been extensively studied and the adsorption isotherms have been developed for only the single metal ion situation, very little attention has been given to the bioremoval and expression of adsorption isotherms of multimetal ions systems. In this study the simultaneous biosorption of copper(II) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single- and dual-metal ion concentrations on the equilibrium uptakes were investigated. In previous studiesmore » the optimum biosorption pH had been determined as 4.0 for copper(II) and as 2.0 for chromium(VI). Multimetal ion biosorption studies were performed at these two pH values. It was observed that the equilibrium uptakes of copper(II) or chromium(VI) ions were changed due to the biosorption pH and the presence of other metal ions. Adsorption isotherms were developed for both single- and dual-metal ions systems at these two pH values, and expressed by the mono- and multicomponent Langmuir and Freundlich adsorption models. Model parameters were estimated by nonlinear regression. It was seen that the adsorption equilibrium data fitted very well to the competitive Freundlich model in the concentration ranges studied.« less

Preliminary results on the development of vacuum brazed joints for cryogenic wind tunnel aerofoil models

NASA Technical Reports Server (NTRS)

Wigley, D. A.; Sandefur, P. G., Jr.; Lawing, P. L.

1981-01-01

The results of initial experiments show that high-strength void-free bonds can be formed by vacuum brazing of stainless steels using copper and nickel-based filler metals. In Nitronic 40, brazed joints have been formed with strengths in excess of the yield strength of the parent metal, and even at liquid nitrogen temperatures the excellent mechanical properties of the parent metal are only slightly degraded. The poor toughness of 15-5 P.H. stainless steel at cryogenic temperatures is lowered even further by the presence of the brazed bonds investigated. It is highly unlikely that the technique would be used for any critical areas of aerofoil models intended for low-temperature service. Nevertheless, the potential advantages of this simplified method of construction still have attractions for use at ambient temperatures.

Cytoprotection by fructose and other ketohexoses during bile salt-induced apoptosis of hepatocytes.

PubMed

Zeid, I M; Bronk, S F; Fesmier, P J; Gores, G J

1997-01-01

Toxic bile salts cause hepatocyte necrosis at high concentrations and apoptosis at lower concentrations. Although fructose prevents bile salt-induced necrosis, the effect of fructose on bile salt-induced apoptosis is unclear. Our aim was to determine if fructose also protects against bile salt-induced apoptosis. Fructose inhibited glycochenodeoxycholate (GCDC)-induced apoptosis in a concentration-dependent manner with a maximum inhibition of 72% +/- 10% at 10 mmol/L. First, we determined if fructose inhibited apoptosis by decreasing adenosine triphosphate (ATP) and intracellular pH (pHi). Although fructose decreased ATP to <25% of basal values, oligomycin (an ATP synthase inhibitor) did not inhibit apoptosis despite decreasing ATP to similar values. Fructose (10 mmol/L) decreased intracellular pH (pHi) by 0.2 U. However, extracellular acidification (pH 6.8), which decreased hepatocyte pHi 0.35 U and is known to inhibit necrosis, actually potentiated apoptosis 1.6-fold. Fructose cytoprotection also could not be explained by induction of bcl-2 transcription or metal chelation. Because we could not attribute fructose cytoprotection to metabolic effects, alterations in the expression of bcl-2, or metal chelation, we next determined if the poorly metabolized ketohexoses, tagatose and sorbose, also inhibited apoptosis; unexpectedly, both ketohexoses inhibited apoptosis. Because bile salt-induced apoptosis and necrosis are inhibited by fructose, these data suggest that similar processes initiate bile salt-induced hepatocyte necrosis and apoptosis. In contrast, acidosis, which inhibits necrosis, potentiates apoptosis. Thus, ketohexose-sensitive pathways appear to initiate both bile salt-induced cell apoptosis and necrosis, whereas dissimilar, pH-sensitive, effector mechanisms execute these two different cell death processes.

Removal Efficiency of the Heavy Metals Zn(II), Pb(II) and Cd(II) by Saprolegnia delica and Trichoderma viride at Different pH Values and Temperature Degrees

PubMed Central

Hashem, Mohamed

2007-01-01

The removal efficiency of the heavy metals Zn, Pb and Cd by the zoosporic fungal species Saprolegnia delica and the terrestrial fungus Trichoderma viride, isolated from polluted water drainages in the Delta of Nile in Egypt, as affected by various ranges of pH values and different temperature degrees,was extensively investigated. The maximum removal efficiency of S. delica for Zn(II) and Cd(II) was obtained at pH 8 and for Pb(II) was at pH 6 whilst the removal efficiency of T. viride was found to be optimum at pH 6 for the three applied heavy metals. Regardless the median lethal doses of the three heavy metals, Zn recorded the highest bioaccumulation potency by S. delica at all pH values except at pH 4, followed by Pb whereas Cd showed the lowest removal potency by the fungal species and vice versa in case of T. viride. The optimum biomass dry weight production by S. delica was found when the fungus was grown in the medium treated with the heavy metal Pb at pH 6, followed by Zn at pH 8 and Cd at pH 8. The optimum biomass dry weight yield by T. viride amended with Zn,Pb and Cd was obtained at pH 6 for the three heavy metals with the maximum value at Zn. The highest yield of biomass dry weight was found when T. viride treated with Cd at all different pH values followed by Pb whilst Zn output was the lowest and this result was reversed in case of S. delica. The maximum removal efficiency and the biomass dry weight production for the three tested heavy metals was obtained at the incubation temperature 20℃ in case of S. delica while it was 25℃ for T. viride. Incubation of T. viride at higher temperatures (30℃ and 35℃) enhanced the removal efficiency of Pb and Cd than low temperatures (15℃ and 20℃) and vice versa in case of Zn removal. At all tested incubation temperatures, the maximum yield of biomass dry weight was attained at Zn treatment by the two tested fungal species. The bioaccumulation potency of S. delica for Zn was higher than that for Pb at all temperature degrees of incubation and Cd bioaccumulation was the lowest whereas T. viride showed the highest removal efficiency for Pb followed by Cd and Zn was the minor of the heavy metals. PMID:24015084

Size, speciation and lability of NOM-metal complexes in hyperalkaline cave dripwater

NASA Astrophysics Data System (ADS)

Hartland, Adam; Fairchild, Ian J.; Lead, Jamie R.; Zhang, Hao; Baalousha, Mohammed

2011-12-01

Transport of trace metals by natural organic matter (NOM) is potentially an important vector for trace metal incorporation in secondary cave precipitates [speleothems], yet little is known about the size distribution, speciation and metal binding properties of NOM in cave dripwaters. A hyperalkaline cave environment (ca. pH 11) was selected to provide information on colloid-metal interactions in cave waters, and to address the lack of high-pH data in natural systems in general. Colloidal (1 nm-1 μm) NOM in hyperalkaline cave dripwater from Poole's Cavern, UK, was characterised by flow field-flow fractionation (FlFFF) coupled to UV and fluorescence detectors and transmission electron microscopy (TEM) coupled to X-ray energy-dispersive spectroscopy (X-EDS); trace-metal lability was examined by diffusive gradients in thin films (DGT). Colloidal aggregates and small particulates (>1 μm) imaged by TEM were morphologically heterogeneous with qualitative elemental compositions (X-EDS spectra; n = 41) consistent with NOM aggregates containing aluminosilicates, and iron and titanium oxides. Globular organic colloids, with diameters between ca. 1 and 10 nm were the most numerous colloidal class and exhibited high UV-absorbance (254 nm) and fluorescence intensity (320:400 nm excitation: emission) in optical regions characteristic of humic-like compounds. Metal binding with humic substances was modelled using the WHAM 6.1 (model VI) and visual MINTEQ 3.0 (NICA-Donnan) speciation codes. At pH 11, both models predicted dominant humic binding of Cu (ca. 100%) and minimal binding of Ni and Co (ca. <1-7%). A DGT depletion experiment (7 days duration) with the hyperalkaline dripwater showed that the available proportion of each metal was much lower than its total concentration. Metal availability for DGT in the initial stages (24 h) was consistent with weaker binding of alkaline earth metals by humic substances (Ba > Sr > V > Cu > Ni > Co), compared to the transition metals. Integrated over the entire experiment, the DGT-available proportion of transition metals (Ni > Cu & V >> Co) differed greatly from the expected hierarchy from WHAM and MINTEQ, indicating unusually strong complexation of Co. Total metal concentrations of Cu, Ni, and Co in raw and filtered PE1 dripwater samples ( n = 53) were well correlated (Cu vs. Ni, R2 = 0.8; Cu vs. Co, R2 = 0.5) and were strongly reduced (> ca. 50%) by filtration at ca. 100 and 1 nm, indicating a common colloidal association. Our results demonstrate that soil-derived colloids reach speleothems, despite transport through a karst zone with potential for adsorption, and that NOM is a dominant complexant of trace metals in high pH speleothem-forming groundwaters.

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

A physicochemical study of Al(+3) interactions with edible seaweed biomass in acidic waters.

PubMed

Lodeiro, Pablo; López-García, Marta; Herrero, Luz; Barriada, José L; Herrero, Roberto; Cremades, Javier; Bárbara, Ignacio; Sastre de Vicente, Manuel E

2012-09-01

In this article, a study of the Al(+3) interactions in acidic waters with biomass of different edible seaweeds: brown (Fucus vesiculosus, Saccorhiza polyschides), red (Mastocarpus stellatus, Gelidium sesquipedale, Chondrus crispus), and green (Ulva rigida, Codium tomentosum), has been performed. The influence of both, the initial concentration of metal and the solution pH, on the Al-uptake capacity of the biomass has been analyzed. From preliminary tests, species Fucus vesiculosus and Gelidium sesquipedale have been selected for a more exhaustive analysis. Sorption kinetic studies demonstrated that 60 min are enough to reach equilibrium. The intraparticle diffusion model has been used to describe kinetic data. Equilibrium studies have been carried out at pH values of 1, 2.5, and 4. Langmuir isotherms showed that the best uptake values, obtained at pH 4, were 33 mg/g for F. vesiculosus and 9.2 mg/g for G. sesquipedale. These edible seaweeds have been found particularly effective in binding aluminum metal ions for most of the conditions tested. Physicochemical data reported at these low pH values could be of interest, not only in modeling aluminum-containing antacids-food pharmacokinetic processes produced in the stomach (pH values 1 to 3) but in remediation studies in acidic waters. Aluminum is thought to be linked to neurological disruptions such as Alzheimer's disease. In this article, the adsorption ability of different types of edible seaweeds toward aluminum has been studied. The choice of low pH values is due to the fact that stomach region is acidic with a pH value between 1 and 3 as a consequence of hydrochloric secretion; so physicochemical data reported in this study could be of interest in modeling drug-food interactions, in particular those referring to aluminum-containing antacids-food pharmacokinetic processes produced in the gastrointestinal tract. © 2012 Institute of Food Technologists®

Sorption mechanisms of metals to graphene oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Showalter, Allison R.; Duster, Thomas A.; Szymanowski, Jennifer E. S.

2016-05-01

Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is anmore » electrostatic attraction between the hydrated Cd+2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems.« less

Substituent Effects on the Coordination Chemistry of Metal-Binding Pharmacophores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Craig, Whitney R.; Baker, Tessa W.; Marts, Amy R.

2017-09-12

A combination of XAS, UV–vis, NMR, and EPR was used to examine the binding of a series of α-hydroxythiones to CoCA. All three appear to bind preferentially in their neutral, protonated forms. Two of the three clearly bind in a monodentate fashion, through the thione sulfur alone. Thiomaltol (TM) appears to show some orientational preference, on the basis of the NMR, while it appears that thiopyromeconic acid (TPMA) retains rotational freedom. In contrast, allothiomaltol (ATM), after initially binding in its neutral form, presumably through the thione sulfur, forms a final complex that is five-coordinate via bidentate coordination of ATM. Onmore » the basis of optical titrations, we speculate that this may be due to the lower initial pKa of ATM (8.3) relative to those of TM (9.0) and TPMA (9.5). Binding through the thione is shown to reduce the hydroxyl pKa by ~0.7 pH unit on metal binding, bringing only ATM’s pKa close to the pH of the experiment, facilitating deprotonation and subsequent coordination of the hydroxyl. The data predict the presence of a solvent-exchangeable proton on TM and TPMA, and Q-band 2-pulse ESEEM experiments on CoCA + TM suggest that the proton is present. ESE-detected EPR also showed a surprising frequency dependence, giving only a subset of the expected resonances at X-band.« less

Differences in soil solution chemistry between soils amended with nanosized CuO or Cu reference materials: implications for nanotoxicity tests.

PubMed

McShane, Heather V A; Sunahara, Geoffrey I; Whalen, Joann K; Hendershot, William H

2014-07-15

Soil toxicity tests for metal oxide nanoparticles often include micrometer-sized oxide and metal salt treatments to distinguish between toxicity from nanometer-sized particles, non-nanometer-sized particles, and dissolved ions. Test result will be confounded if each chemical form has different effects on soil solution chemistry. We report on changes in soil solution chemistry over 56 days-the duration of some standard soil toxicity tests-in three soils amended with 500 mg/kg Cu as nanometer-sized CuO (nano), micrometer-sized CuO (micrometer), or Cu(NO3)2 (salt). In the CuO-amended soils, the log Cu2+ activity was initially low (minimum -9.48) and increased with time (maximum -5.20), whereas in the salt-amended soils it was initially high (maximum -4.80) and decreased with time (minimum -6.10). The Cu2+ activity in the nano-amended soils was higher than in the micrometer-amended soils for at least the first 11 days, and lower than in the salt-amended soils for at least 28 d. The pH, and dissolved Ca and Mg concentrations in the CuO-amended soils were similar, but the salt-amended soils had lower pH for at least 14 d, and higher Ca and Mg concentrations throughout the test. Soil pretreatments such as leaching and aging prior to toxicity tests are suggested.

Application of a mixed culture of adapted acidophilic bacteria in two-step bioleaching of spent lithium-ion laptop batteries

NASA Astrophysics Data System (ADS)

Heydarian, Ahmad; Mousavi, Seyyed Mohammad; Vakilchap, Farzane; Baniasadi, Mahsa

2018-02-01

The rapid increase in the production of electrical and electronic equipment, along with higher consumption of these products, has caused defective and obsolete equipment to accumulate in the environment. In this research, bioleaching of spent lithium-ion batteries (LIBs) used in laptops is carried out under two-step condition based on the bacterial activities of a mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. First, the best inoculum ratio of two acidophilic bacteria for the mixed culture is obtained. Next, adaptation is carried out successfully and the solid-to-liquid ratio reaches 40 g L-1. Response surface methodology is utilized to optimize the effective variables of initial pH, iron sulfate and sulfur concentrations. The maximum recovery of metal is about 99.2% for Li, 50.4% for Co and 89.4% for Ni under optimum conditions of 36.7 g L-1 iron sulfate concentration, 5.0 g L-1 sulfur concentration and initial pH of 1.5 for the best inoculum ratio of 3/2. Results of FE-SEM, XRD and FTIR analysis before and after bioleaching confirm that bacterial activity is a promising and effective route for metal recovery from spent LIBs. Toxicity assessment tests demonstrate the suitability of the bioleached residual as a nonhazardous material that meets environmental limitations for safe disposal.

Method for removing metals from a cleaning solution

DOEpatents

Deacon, Lewis E.

2002-01-01

A method for removing accumulated metals from a cleaning solution is provided. After removal of the metals, the cleaning solution can be discharged or recycled. The process manipulates the pH levels of the solution as a means of precipitating solids. Preferably a dual phase separation at two different pH levels is utilized.

Role of direct electron-phonon coupling across metal-semiconductor interfaces in thermal transport via molecular dynamics.

PubMed

Lin, Keng-Hua; Strachan, Alejandro

2015-07-21

Motivated by significant interest in metal-semiconductor and metal-insulator interfaces and superlattices for energy conversion applications, we developed a molecular dynamics-based model that captures the thermal transport role of conduction electrons in metals and heat transport across these types of interface. Key features of our model, denoted eleDID (electronic version of dynamics with implicit degrees of freedom), are the natural description of interfaces and free surfaces and the ability to control the spatial extent of electron-phonon (e-ph) coupling. Non-local e-ph coupling enables the energy of conduction electrons to be transferred directly to the semiconductor/insulator phonons (as opposed to having to first couple to the phonons in the metal). We characterize the effect of the spatial e-ph coupling range on interface resistance by simulating heat transport through a metal-semiconductor interface to mimic the conditions of ultrafast laser heating experiments. Direct energy transfer from the conduction electrons to the semiconductor phonons not only decreases interfacial resistance but also increases the ballistic transport behavior in the semiconductor layer. These results provide new insight for experiments designed to characterize e-ph coupling and thermal transport at the metal-semiconductor/insulator interfaces.

Alkali metals in addition to acidic pH activate the EvgS histidine kinase sensor in Escherichia coli.

PubMed

Eguchi, Yoko; Utsumi, Ryutaro

2014-09-01

Two-component signal transduction systems (TCSs) in bacteria perceive environmental stress and transmit the information via phosphorelay to adjust multiple cellular functions for adaptation. The EvgS/EvgA system is a TCS that confers acid resistance to Escherichia coli cells. Activation of the EvgS sensor initiates a cascade of transcription factors, EvgA, YdeO, and GadE, which induce the expression of a large group of acid resistance genes. We searched for signals activating EvgS and found that a high concentration of alkali metals (Na(+), K(+)) in addition to low pH was essential for the activation. EvgS is a histidine kinase, with a large periplasmic sensor region consisting of two tandem PBPb (bacterial periplasmic solute-binding protein) domains at its N terminus. The periplasmic sensor region of EvgS was necessary for EvgS activation, and Leu152, located within the first PBPb domain, was involved in the activation. Furthermore, chimeras of EvgS and PhoQ histidine kinases suggested that alkali metals were perceived at the periplasmic sensor region, whereas the cytoplasmic linker domain, connecting the transmembrane region and the histidine kinase domain, was required for low-pH perception. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Enhanced recovery of valuable metals from spent lithium-ion batteries through optimization of organic acids produced by Aspergillus niger.

PubMed

Bahaloo-Horeh, Nazanin; Mousavi, Seyyed Mohammad

2017-02-01

In the present study, spent medium bioleaching method was performed using organic acids produced by Aspergillus niger to dissolve Ni, Co, Mn, Li, Cu and Al from spent lithium-ion batteries (LIBs). Response surface methodology was used to investigate the effects and interactions between the effective factors of sucrose concentration, initial pH, and inoculum size to optimize organic acid production. Maximum citric acid, malic acid, and gluconic acid concentrations of 26,478, 1832.53 and 8433.76ppm, respectively, and a minimum oxalic acid concentration of 305.558ppm were obtained under optimal conditions of 116.90 (gl -1 ) sucrose concentration, 3.45% (vv -1 ) inoculum size, and a pH value of 5.44. Biogenically-produced organic acids are used for leaching of spent LIBs at different pulp densities. The highest metal recovery of 100% Cu, 100% Li, 77% Mn, and 75% Al occurred at 2% (wv -1 ) pulp density; 64% Co and 54% Ni recovery occurred at 1% (wv -1 ) pulp density. The bioleaching of metals from spent LIBs can decrease the environmental impact of this waste. The results of this study suggest that the process can be used for large scale industrial purposes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Heavy metal, pH, and total solid content of maple sap and syrup produced in eastern Canada.

PubMed

Robinson, A R; MacLean, K S; MacConnell, H M

1989-01-01

Maple sap and syrups in eastern Canada were analyzed for pH, total solids, and the heavy metals Cu, Fe, Pb, and Zn. The levels of heavy metals found were within the range normally contained in food and water samples except for Pb. The concentration factor found in reducing sap to syrup did not reflect the same concentration change for the measured parameters. This indicates removal or conversion of heavy metals and organic acids with the sugar sands. There was no statistical difference among provinces with respect to the heavy metal, pH, and total solids content of sap. The only significant difference in syrup occurred with Cu and this appeared to be the result of the processing procedure. As the season progressed, the Cu, Pb, pH, and total solids content of the sap decreased while Zn increased and Fe showed little change. Syrups reflected a similar change. Statistical differences occurred in sap composition among sites within each province.

Release of metals from metal-amended soil treated with a sulfosuccinamate surfactant: effects of surfactant concentration, soil/solution ratio, and pH.

PubMed

Hernández-Soriano, Maria del Carmen; Peña, Aránzazu; Dolores Mingorance, Ma

2010-01-01

Anionic surfactants, mainly sulfosuccinamates, can be found in soils as the result of sludge application, wastewater irrigation, and remediation processes. Relatively high concentrations of surfactants together with multimetals can represent an environmental risk. A study was performed to assess the potential of the anionic surfactant Aerosol 22 (A22) for release of Cd, Cu, Pb, and Zn from a metal-amended soil representative of a Mediterranean area. Metal desorption was performed by batch experiments and release kinetics were assessed. Response surface methodology was applied to determine the influence of A22 concentration and the surfactant/soil ratio, as extraction key factors. An increase in solution/soil ratio to 100 (mL g(-1)) caused higher metal release. Leaching predictions found Pb to have the lowest and Cd the highest hazard. Metal release was highly dependent on pH. When extraction was made at pH less than 7, low or negligible amounts of metals were leached, whereas an increase to pH 7 caused desorption rates of 50 to 55% for Cd, Cu, and Zn but only 35% for Pb. Complexed metal-carboxylic groups from A22 were mainly responsible for its higher extractive capacity, especially of Cd and Cu.

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Effects of calcium, magnesium, and sodium on alleviating cadmium toxicity to Hyalella azteca

USGS Publications Warehouse

Jackson, B.P.; Lasier, P.J.; Miller, W.P.; Winger, P.V.

2000-01-01

Toxicity of trace metal ions to aquatic organisms, arising through either anthropogenic inputs or acidification of surface waters, continues to be both a regulatory and environmental problem. It is generally accepted that the free metal ion is the major toxic species (Florence et a1.,1992) and that inorganic or organic complexation renders the metal ion non-bioavailable (Meador, 1991, Galvez and Wood, 1997). However, water chemistry parameters such as alkalinity, hardness, dissolved organic carbon and pH influence metal ion toxicity either directly by lowering free metal ion concentration or indirectly through synergistic or antagonistic effects. Alkalinity and salinity can affect the speciation of metal ions by increasing ion-pair formation, thus decreasing free metal ion concentration. For example, Cu was found to be less toxic to rainbow trout in waters of high alkalinity (Miller and Mackay, 1980), due to formation of CuCO3 ion pair, and corresponding reduction in free Cu2+ concentration. The influence of salinity on the toxicity of cadmium to various organisms has been demonstrated in a number of studies (Bervoets et al., 1995, Hall et al., 1995, Lin and Dunson, 1993, Blust et al., 1992). In all these studies the apparent toxicity of cadmium was lowered as salinity was increased due to increased formation of CdC1+ and CDCl2 aqueous complexes that are non-toxic or of much lower toxicity than the free Cd2+ ion. Changes in pH exert both a biological and chemical effect on metal ion toxicity (Campbell and Stokes, 1985). Low pH favors greater metal ion solubility, and, in the absence of complexing ions, reduced speciation of the metal ion, which tends to increase toxicity compared to higher pH. However, Iow pH also enhances competition between H+ and metal ion for cell surface binding sites, which tends to decrease metal ion toxicity.

Effect of aeration rate, moisture content and composting period on availability of copper and lead during pig manure composting.

PubMed

Shen, Yujun; Zhao, Lixin; Meng, Haibo; Hou, Yueqing; Zhou, Haibin; Wang, Fei; Cheng, Hongsheng; Liu, Hongbin

2016-06-01

Pollution by heavy metals, such as copper and lead, has become a limiting factor for the land application of faecal manures, such as pig manure. This study was conducted to investigate the influence of composting process parameters, including aeration rate, moisture content and composting period, on the distribution of heavy metal species during composting, and to select an optimal parameter for copper and lead inactivation. Results showed that the distribution ratios of exchangeable fractions of copper and lead had a bigger decrease under conditions of aeration rate, 0.1 m(3) min(-1) m(-3), an initial moisture content of 65% and composting period of 50 days. Suboptimal composting process conditions could lead to increased availability of heavy metals. Statistical analysis indicated that the aeration rate was the main factor affecting copper and lead inactivation, while the effects of moisture content and composting period were not significant. The rates of reduction of copper-exchangeable fractions and lead-exchangeable fractions were positively correlated with increased pH. The optimal parameters for reducing heavy metal bioavailability during pig manure composting were aeration rate, 0.1 m(3) min(-1) m(-3), initial moisture content, 65%, and composting period, 20 days. © The Author(s) 2016.

Heavy metals alter the electrokinetic properties of bacteria, yeasts, and clay minerals.

PubMed Central

Collins, Y E; Stotzky, G

1992-01-01

The electrokinetic patterns of four bacterial species (Bacillus subtilis, Bacillus megaterium, Pseudomonas aeruginosa, and Agrobacterium radiobacter), two yeasts (Saccharomyces cerevisiae and Candida albicans), and two clay minerals (montmorillonite and kaolinite) in the presence of the chloride salts of the heavy metals, Cd, Cr, Cu, Hg, Ni, Pb, and Zn, and of Na and Mg were determined by microelectrophoresis. The cells and kaolinite were net negatively charged at pH values above their isoelectric points (pI) in the presence of Na, Mg, Hg, and Pb at an ionic strength (mu) of 3 x 10(-4); montmorillonite has no pI and was net negatively charged at all pH values in the presence of these metals. However, the charge of some bacteria, S. cerevisiae, and kaolinite changed to a net positive charge (charge reversal) in the presence of Cd, Cr, Cu, Ni, and Zn at pH values above 5.0 (the pH at which charge reversal occurred differed with the metal) and then, at higher pH values, again became negative. The charge of the bacteria and S. cerevisiae also reversed in solutions of Cu and Ni with a mu of greater than 3 x 10(-4), whereas there was no reversal in solutions with a mu of less than 3 x 10(-4). The clays became net positively charged when the mu of Cu was greater than 3 x 10(-4) and that of Ni was greater than 1.5 x 10(-4). The charge of the cells and clays also reversed in solutions containing both Mg and Ni or both Cu and Ni (except montmorillonite) but not in solutions containing both Mg and Cu (except kaolinite) (mu = 3 x 10(-4)). The pIs of the cells in the presence of the heavy metals were at either higher or lower pH values than in the presence of Na and Mg. Exposure of the cells to the various metals at pH values from 2 to 9 for the short times (ca. 10 min) required to measure the electrophoretic mobility did not affect their viability. The specific adsorption on the cells and clays of the hydrolyzed species of some of the heavy metals that formed at higher pH values was probably responsible for the charge reversal. These results suggest that the toxicity of some heavy metals to microorganisms varies with pH because the hydrolyzed speciation forms of these metals, which occur at higher pH values, bind on the cell surface and alter the net charge of the cell.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:1622229

Optimization of exopolysaccharide production from Pseudomonas stutzeri AS22 and examination of its metal-binding abilities.

PubMed

Maalej, H; Hmidet, N; Boisset, C; Buon, L; Heyraud, A; Nasri, M

2015-02-01

To investigate the effect of culture conditions and medium components on exopolysaccharide (EPS) production by Pseudomonas stutzeri AS22 and to access the EPS performance as a metal-binding exopolysaccharide. The EPS production conditions of Ps. stutzeri AS22 in submerged culture were optimized using two approaches for EPS quantification, and its metal-binding capacity was evaluated using both single and mixed metal ions systems. Maximum EPS level was achieved after 24 h of incubation at 30°C with an initial pH of 8.0, 250 rev min(-1) stirring level and 10% inoculum size. 50 g l(-1) starch, 5 g l(-1) yeast extract, 0.5 g l(-1) NaCl, 1.4 g l(-1) K2 HPO4, 0.4 g l(-1) MgSO4, 0.4 g l(-1) CaCl2 and 1 g l(-1) mannose were found to be the most suitable carbon, nitrogen, mineral and additional carbohydrate sources, respectively. From metal-binding experiments, the crude EPS showed interesting metal adsorption capacity adopting the order Pb > Co > Fe > Cu > Cd. Lead was preferentially biosorbed with a maximal uptake of 460 mg g(-1) crude EPS. Under the optimal culture requirements, EPS level reached 10.2 g l(-1) after 24 h of fermentation, seven times more than the production under initial conditions. According to the metal-binding assay, the crude EPS has potential to be used as a novel biosorbent in the treatment of heavy metals-contaminated water. Our results are interesting in terms of yield as well as efficiency for the potential use of the Ps. stutzeri exopolysaccharide as a metal-absorbent polymer in the bioremediation field. © 2014 The Society for Applied Microbiology.

Can gamma irradiation during radiotherapy influence the metal release process for biomedical CoCrMo and 316L alloys?

PubMed

Wei, Zheng; Edin, Jonathan; Karlsson, Anna Emelie; Petrovic, Katarina; Soroka, Inna L; Odnevall Wallinder, Inger; Hedberg, Yolanda

2018-02-09

The extent of metal release from implant materials that are irradiated during radiotherapy may be influenced by irradiation-formed radicals. The influence of gamma irradiation, with a total dose of relevance for radiotherapy (e.g., for cancer treatments) on the extent of metal release from biomedical stainless steel AISI 316L and a cobalt-chromium alloy (CoCrMo) was investigated in physiological relevant solutions (phosphate buffered saline with and without 10 g/L bovine serum albumin) at pH 7.3. Directly after irradiation, the released amounts of metals were significantly higher for irradiated CoCrMo as compared to nonirradiated CoCrMo, resulting in an increased surface passivation (enhanced passive conditions) that hindered further release. A similar effect was observed for 316L showing lower nickel release after 1 h of initially irradiated samples as compared to nonirradiated samples. However, the effect of irradiation (total dose of 16.5 Gy) on metal release and surface oxide composition and thickness was generally small. Most metals were released initially (within seconds) upon immersion from CoCrMo but not from 316L. Albumin induced an increased amount of released metals from AISI 316L but not from CoCrMo. Albumin was not found to aggregate to any greater extent either upon gamma irradiation or in the presence of trace metal ions, as determined using different light scattering techniques. Further studies should elucidate the effect of repeated friction and fractionated low irradiation doses on the short- and long term metal release process of biomedical materials. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2018. © 2018 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc.

Treatment of metal-contaminated wastewater: a comparison of low-cost biosorbents.

PubMed

Akunwa, N K; Muhammad, M N; Akunna, J C

2014-12-15

This study aimed to identify some optimum adsorption conditions for the use of low-cost adsorbent, seaweed (Ascophyllum nodosum), sawdust and reed plant (Phragmites australis) root, in the treatment of metal contaminated wastewater for the removal of cadmium, chromium and lead. The effect of pH on the absorption capacity of each of these biosorbents was found to be significant and dependent on the metal being removed. Post-adsorption FTIR analysis showed significant binding activities at the nitro NO groups site in all biosorbents, especially for lead. Competitive metal binding was found to have possibly affected the adsorption capacity for chromium by A. nodosum more than it affected sawdust and P. australis root. Adsorption is believed to take place mainly by ion exchange particularly at low pH values. P. australis root exhibited the highest adsorption for chromium at pH 2, cadmium at pH 10 and lead at pH 7. A. nodosum seaweed species demonstrated the highest adsorption capacity of the three biosorbents used in the study, for cadmium at pH 7 and for lead at pH 2. Sawdust proved to be an efficient biosorbent for lead removal only at pH 7 and 10. No significant effect of temperature on adsorption capacity was observed, particularly for cadmium and lead removal. Copyright © 2014 Elsevier Ltd. All rights reserved.

Simultaneous bioaccumulation of multiple metals from electroplating effluent using Aspergillus lentulus.

PubMed

Mishra, Abhishek; Malik, Anushree

2012-10-15

Toxic impacts of heavy metals in the environment have lead to intensive research on various methods of heavy metal remediation. However, in spite of abundant work on heavy metals removal from simple synthetic solutions, a very few studies demonstrate the potential of microbial strains for the treatment of industrial effluents containing mixtures of metals. In the present study, the efficiency of an environmental isolate (Aspergillus lentulusFJ172995), for simultaneous removal of chromium, copper and lead from a small-scale electroplating industry effluent was investigated. Initial studies with synthetic solutions infer that A. lentulus has a remarkable tolerance against Cr, Cu, Pb and Ni. During its growth, a significant bioaccumulation of individual metal was recorded. After 5 d of growth, the removal of metals from synthetic solutions followed the trend Pb(2+) (100%) > Cr(3+) (79%) > Cu(2+) (78%), > Ni(2+) (42%). When this strain was applied to the treatment of multiple metal containing electroplating effluent (after pH adjustment), the metal concentrations decreased by 71%, 56% and 100% for Cr, Cu and Pb, respectively within 11 d. Based on our results, we propose that the simultaneous removal of hazardous metals from industrial effluents can be accomplished using A. lentulus. Copyright © 2012 Elsevier Ltd. All rights reserved.

2,4-Dinitrophenylhydrazine functionalized sodium dodecyl sulfate-coated magnetite nanoparticles for effective removal of Cd(II) and Ni(II) ions from water samples.

PubMed

Sobhanardakani, Soheil; Zandipak, Raziyeh

2015-07-01

2,4-Dinitrophenylhydrazine immobilized on sodium dodecyl sulfate (SDS)-coated magnetite and was used for removal of Cd(II) and Ni(II) ions from aqueous solution. The prepared product was characterized by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The size of the nanoparticles according to SEM was obtained around 20-35 nm. In batch tests, the effects of pH, contact time, initial metal concentration, and temperature were studied. The kinetic and equilibrium data were modeled with recently developed models. The adsorption kinetics and isotherms were well fitted by the fractal-like pseudo-second-order model and Langmuir-Freundlich model, respectively. Maximum adsorption capacity by this adsorbent is 255.1 mg g(-1) for Cd(II) ion and 319.6 mg g(-1) for Ni(II) ion at pH 7.0 and 25 °C. The method was successfully applied to the removal of metal cations in real samples (tap water, river water, and petrochemical wastewater).

Bioremediation of Cd by strain GZ-22 isolated from mine soil based on biosorption and microbially induced carbonate precipitation.

PubMed

Zhao, Yue; Yao, Jun; Yuan, Zhimin; Wang, Tianqi; Zhang, Yiyue; Wang, Fei

2017-01-01

Microbially induced carbonate precipitation (MICP) is an emerging and promising bioremediation technology to restore the environment polluted by heavy metals. Carbonate-biomineralization microbe can immobilize heavy metals from mobile species into stable crystals. In the present manuscript, laboratory batch studies were conducted to evaluate the Cd removal ability based on biosorption and MICP, using carbonate-biomineralization microbe GZ-22 isolated from a mine soil. This strain was identified as a Bacillus sp. according to 16S rDNA gene sequence analysis. Results of batch experiments revealed that MICP of the strain GZ-22 showed a greater potential to remove Cd than biomass biosorption under different impact factors such as pH, initial Cd concentration, and contact time. The optimum pH for MICP was 6 (50.34 %), while for biomass biosorption, it was 5 (38.81 %). When the initial concentration of Cd was 10 mg/L, removal efficiency induced by MICP was 53.06 % after 3 h, which was about 11 % greater than the removal efficiency induced by adsorption. The Cd removal efficiency increased as reaction time. The maximum removal efficiency based on MICP can reach 60.72 % at 10 mg/L for 48 h compared with 56.27 % by biosorption. X-ray diffractomer (XRD) revealed that Cd was transformed into CdCO 3 by MICP of GZ-22. The present illustrated that the carbonate-biomineralization microbe GZ-22 can offer an effective and eco-friendly approach to immobilize soluble Cd and that MICP may play an important role in heavy metal bioremediation.

URANIUM PRECIPITATION PROCESS

DOEpatents

Thunaes, A.; Brown, E.A.; Smith, H.W.; Simard, R.

1957-12-01

A method for the recovery of uranium from sulfuric acid solutions is described. In the present process, sulfuric acid is added to the uranium bearing solution to bring the pH to between 1 and 1.8, preferably to about 1.4, and aluminum metal is then used as a reducing agent to convert hexavalent uranium to the tetravalent state. As the reaction proceeds, the pH rises amd a selective precipitation of uranium occurs resulting in a high grade precipitate. This process is an improvement over the process using metallic iron, in that metallic aluminum reacts less readily than metallic iron with sulfuric acid, thus avoiding consumption of the reducing agent and a raising of the pH without accomplishing the desired reduction of the hexavalent uranium in the solution. Another disadvantage to the use of iron is that positive ferric ions will precipitate with negative phosphate and arsenate ions at the pH range employed.

Metal release from contaminated coastal sediments under changing pH conditions: Implications for metal mobilization in acidified oceans.

PubMed

Wang, Zaosheng; Wang, Yushao; Zhao, Peihong; Chen, Liuqin; Yan, Changzhou; Yan, Yijun; Chi, Qiaoqiao

2015-12-30

To investigate the impacts and processes of CO2-induced acidification on metal mobilization, laboratory-scale experiments were performed, simulating the scenarios where carbon dioxide was injected into sediment-seawater layers inside non-pressurized chambers. Coastal sediments were sampled from two sites with different contamination levels and subjected to pre-determined pH conditions. Sediment samples and overlying water were collected for metal analysis after 10-days. The results indicated that CO2-induced ocean acidification would provoke increased metal mobilization causing adverse side-effects on water quality. The mobility of metals from sediment to the overlying seawater was correlated with the reduction in pH. Results of sequential extractions of sediments illustrated that exchangeable metal forms were the dominant source of mobile metals. Collectively, our data revealed that high metal concentrations in overlying seawater released from contaminated sediments under acidic conditions may strengthen the existing contamination gradients in Maluan Bay and represent a potential risk to ecosystem health in coastal environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

PEROXOTITANATE- AND MONOSODIUM METAL-TITANATE COMPOUNDS AS INHIBITORS OF BACTERIAL GROWTH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hobbs, D.

2011-01-19

Sodium titanates are ion-exchange materials that effectively bind a variety of metal ions over a wide pH range. Sodium titanates alone have no known adverse biological effects but metal-exchanged titanates (or metal titanates) can deliver metal ions to mammalian cells to alter cell processes in vitro. In this work, we test a hypothesis that metal-titanate compounds inhibit bacterial growth; demonstration of this principle is one prerequisite to developing metal-based, titanate-delivered antibacterial agents. Focusing initially on oral diseases, we exposed five species of oral bacteria to titanates for 24 h, with or without loading of Au(III), Pd(II), Pt(II), and Pt(IV), andmore » measuring bacterial growth in planktonic assays through increases in optical density. In each experiment, bacterial growth was compared with control cultures of titanates or bacteria alone. We observed no suppression of bacterial growth by the sodium titanates alone, but significant (p < 0.05, two-sided t-tests) suppression was observed with metal-titanate compounds, particularly Au(III)-titanates, but with other metal titanates as well. Growth inhibition ranged from 15 to 100% depending on the metal ion and bacterial species involved. Furthermore, in specific cases, the titanates inhibited bacterial growth 5- to 375-fold versus metal ions alone, suggesting that titanates enhanced metal-bacteria interactions. This work supports further development of metal titanates as a novel class of antibacterials.« less

Recovery of critical and value metals from mobile electronics enabled by electrochemical processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tedd E. Lister; Peiming Wang; Andre Anderko

2014-10-01

Electrochemistry-based schemes were investigated as a means to recover critical and value metals from scrap mobile electronics. Mobile electronics offer a growing feedstock for replenishing value and critical metals and reducing need to exhaust primary sources. The electrorecycling process generates oxidizing agents at an anode to dissolve metals from the scrap matrix while reducing dissolved metals at the cathode. The process uses a single cell to maximize energy efficiency. E vs pH diagrams and metals dissolution experiments were used to assess effectiveness of various solution chemistries. Following this work, a flow chart was developed where two stages of electrorecycling weremore » proposed: 1) initial dissolution of Cu, Sn, Ag and magnet materials using Fe+3 generated in acidic sulfate and 2) final dissolution of Pd and Au using Cl2 generated in an HCl solution. Experiments were performed using a simulated metal mixture equivalent to 5 cell phones. Both Cu and Ag were recovered at ~ 97% using Fe+3 while leaving Au and Pd intact. Strategy for extraction of rare earth elements (REE) from dissolved streams is discussed as well as future directions in process development.« less

Determination of trace metals in drinking water using solid-phase extraction disks and X-ray fluorescence spectrometry.

PubMed

Hou, Xiandeng; Peters, Heather L; Yang, Zheng; Wagner, Karl A; Batchelor, James D; Daniel, Meredith M; Jones, Bradley T

2003-03-01

A convenient method is described for monitoring Cd, Ni, Cu, and Pb at trace levels in drinking water samples. These metals are preconcentrated on a chelating solid-phase extraction disk and then determined by X-ray fluorescence spectrometry. The method tolerates a wide pH range (pH 6-14) and a large amount of alkaline and alkaline earth elements. The preconcentration factor is well over 1600, assuming a 1 L water sample volume. The limits of detection for Cd, Ni, Cu, and Pb are 3.8, 0.6, 0.4, and 0.3 ng/mL, respectively. These are well below the federal maximum contaminant level values, which are 5, 100, 1300, and 15 ng/mL, respectively. The proposed method has many advantages including ease of operation, multielement capability, nondestructiveness, high sensitivity, and relative cost efficiency. The solid-phase extraction step can be conducted in the field and then the disks can be mailed to a laboratory for the analysis, eliminating the cost of transporting large volumes of water samples. Furthermore, the color of the used extraction disk provides an initial estimate of the degree of contamination for some transition metals (for example, Ni and Cu). Thus, the overall cost for analysis of metals in drinking water can be minimized by implementing the method, and small water supply companies with limited budgets will be better able to comply with the Safe Drinking Water Act.

An experimental and quantum chemical study of removal of utmostly quantified heavy metals in wastewater using coconut husk: A novel approach to mechanism.

PubMed

Malik, Reena; Dahiya, Shefali; Lata, Suman

2017-05-01

The present study explores the uptake capacity of low cost agricultural waste i.e.Unmodified Coconut (Cocos nucifera L.) Husk for the removal of heavy metal (Pb 2+ , Cu 2+ , Ni 2+ and Zn 2+ ) ions from industrial wastewater. The effect of various operational parameters such as adsorbent dose, high initial metal concentration (100mg/L-500mg/L), pH, temperature and agitation time on the removal of these ions has been investigated using batch experiments. The results showed that maximum uptake through adsorption occurred at 443.0mg/g (88.6%) for Cu, for Ni with 404.5mg/g (80.9%), 362.2mg/g (72.4%) for Pb 2+ and 338.0mg/g (67.6%) for Zn 2+ ion simultaneously. The adsorption capacity was found to be sensitive to the amount of adsorbent, heavy metal ion concentration, pH, temperature and contact time. The experimental statistics have been correlated and interpreted by a new proposed mechanism based upon quantum chemical study of the adsorbent. The theoretical study using quantum has provided the rich electron donation sites of Coconut Husk and hence proposed mechanism of removal. The various adsorption isotherms (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Flory-Huggins), SEM study and physico-chemical properties of the ions suit well to the observed data. Copyright © 2017 Elsevier B.V. All rights reserved.

The Role of Magmatic Volatile Input, Near-surface Seawater Entrainment and Sulfide Deposition in Regulating Metal Concentrations Within Manus Basin Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Craddock, P. R.; Tivey, M. K.; Seewald, J. S.; Rouxel, O.; Bach, W.

2007-12-01

Analyses of Fe, Mn, Cu, Zn, Pb, Ag, Cd, Co and Sb in vent fluid samples from four hydrothermal systems in the Manus back-arc basin, Papua New Guinea, were carried out by ICP-MS. Vienna Woods is located on the well- defined, basalt-dominated Manus Spreading Center, while the other systems are hosted in felsic volcanics on the Pual Ridge (PACMANUS), within a caldera (DESMOS), and on volcanic cones (SuSu Knolls). Metal concentrations were coupled with other fluid data (pH, SO4, Ca, H2S) to discriminate effects of deep- seated water-rock reaction and magmatic volatile input from near surface seawater entrainment, mixing, and consequent mineral precipitation and metal remobilization. Both magmatic volatile input (e.g. SO2, HCl, HF) and sulfide precipitation can increase fluid acidity and thus affect the aqueous mobility of metals. At Vienna Woods, 280°C end-member (Mg = 0) fluids have high pH (>4.2) and low metal contents (Fe <160 uM, Cu <10 uM, Zn <40 uM) relative to most mid-ocean ridge (MOR) vent fluids. The high pH and lack of evidence for magmatic volatile input are consistent with fluid compositions regulated by subsurface seawater- basalt/andesite reactions. Despite low aqueous Zn concentrations, Zn-rich (wurtzite-lined) chimneys are common at Vienna Woods active vents, reflecting deposition from fluids characterized by low Fe and Cu and high pH. At PACMANUS, black smoker fluids (T >300°C, pH ~ 2.7) are enriched in sulfide-forming metals by an order of magnitude relative to Vienna Woods fluids. Enrichments at PACMANUS reflect efficient leaching of metals at low pH, with the lower pH likely a result of input of magmatic volatiles. In addition, some vents fluids show clear evidence for seawater entrainment, subsurface precipitation of Cu-Fe-sulfides and preferential remobilization of Zn-sulfides (lower T, non-zero Mg, lower Fe, Cu, H2S and pH (2.3-2.4), but higher Zn, Pb, Cd and Ag, compared to black smokers). The higher metal concentrations and lower pH of fluids from PACMANUS versus Vienna Woods are reflected in chimney deposit compositions with Zn-poor sulfide linings composed of Cu-Fe-sulfides and As-Sb-sulfosalts in high T and lower T vents, respectively. At DESMOS caldera, fluid data suggest extensive magmatic volatile input (e.g. pH <1.5, elevated F and SO4) but lesser reaction with the basement felsic rocks (low Li, Rb, Mn). Sampled "acid-sulfate" fluids are low temperature (T ~180°C) with Mg >46 mM, and very high concentrations of some metals for these Mg concentrations (Fe >5 mM, Zn >50 - 400 uM). At SuSu Knolls, vent fluid compositions similar to those at both PACMANUS and DESMOS are observed. Smoker fluids have high but variable metal concentrations of similar magnitude to PACMANUS. Acid-sulfate fluids from North Su have low pH (<2), non-zero Mg (>40 mM), and high Fe and Zn concentrations, similar to DESMOS fluids. At SuSu Knolls, fluid compositions reflect either high temperature water-rock reaction (smoker fluids) or magmatic volatile input (acid-sulfate fluids). As at PACMANUS, chimney deposits that correspond to venting fluids are Cu-Fe-As-Sb-rich and Zn-poor, likely reflecting deposition from low pH, high Cu and Fe fluids.

Characterization, sorption, and exhaustion of metal oxide nanoparticles as metal adsorbents

NASA Astrophysics Data System (ADS)

Engates, Karen Elizabeth

Safe drinking water is paramount to human survival. Current treatments do not adequately remove all metals from solution, are expensive, and use many resources. Metal oxide nanoparticles are ideal sorbents for metals due to their smaller size and increased surface area in comparison to bulk media. With increasing demand for fresh drinking water and recent environmental catastrophes to show how fragile water supplies are, new approaches to water conservation incorporating new technologies like metal oxide nanoparticles should be considered as an alternative method for metal contaminant adsorbents from typical treatment methods. This research evaluated the potential of manufactured iron, anatase, and aluminum nanoparticles (Al2O3, TiO2, Fe2O3) to remove metal contaminants (Pb, Cd, Cu, Ni, Zn) in lab-controlled and natural waters in comparison to their bulk counterparts by focusing on pH, contaminant and adsorbent concentrations, particle size, and exhaustive capabilities. Microscopy techniques (SEM, BET, EDX) were used to characterize the adsorbents. Adsorption experiments were performed using 0.01, 0.1, or 0.5 g/L nanoparticles in pH 8 solution. When results were normalized by mass, nanoparticles adsorbed more than bulk particles but when surface area normalized the opposite was observed. Adsorption was pH-dependent and increased with time and solid concentration. Aluminum oxide was found to be the least acceptable adsorbent for the metals tested, while titanium dioxide anatase (TiO2) and hematite (alpha-Fe2O3) showed great ability to remove individual and multiple metals from pH 8 and natural waters. Intraparticle diffusion was likely part of the complex kinetic process for all metals using Fe2O3 but not TiO 2 nanoparticles within the first hour of adsorption. Adsorption kinetics for all metals tested were described by a modified first order rate equation used to consider the diminishing equilibrium metal concentrations with increasing metal oxides, showing faster adsorption rates for nanoparticles compared to bulk particles. Isotherms were best fit with most correlations of r=0.99 or better using the Langmuir-Freundlich equation which describes a heterogeneous surface with monolayer adsorption. Calculated rate constants and distribution coefficients (Kd) showed TiO2 nanoparticles were very good sorbents and more rapid in removing metals than other nanoparticles studied here and reported in the literature. Desorption studies concluded Pb, Cd, and Zn appear to be irreversibly sorbed to TiO2 surfaces at pH 8. TiO2 and Fe2O3 nanoparticles were capable of multiple metal loadings, with exhaustion for both adsorbents at pH 6. Exhaustion studies at pH 8 showed hematite exhausted after four consecutive cycles while anatase showed no exhaustion after 8 cycles. Their bulk counterparts exhausted in earlier cycles indicating the lack of ability to adsorb much of the multiple metals in solution. The increased surface area of TiO2 and Fe 2O3 nanoparticles, coupled with strong adsorption at the pH of most natural waters and resistance to desorption of some metals, may offer a potential remediation method for removal of metals from water in the future.

Biotherapeutic formulation factors affecting metal leachables from stainless steel studied by design of experiments.

PubMed

Zhou, Shuxia; Evans, Brad; Schöneich, Christian; Singh, Satish K

2012-03-01

Trace amounts of metals are inevitably present in biotherapeutic products. They can arise from various sources. The impact of common formulation factors such as protein concentration, antioxidant, metal chelator concentration and type, surfactant, pH, and contact time with stainless steel on metal leachables was investigated by a design of experiments approach. Three major metal leachables, iron, chromium, and nickel were monitored by inductively coupled plasma-mass spectrometry. It was observed that among all the tested factors, contact time, metal chelator concentration, and protein concentration were statistically significant factors with higher temperature resulting in higher levels of leached metals. Within a pH range of 5.5-6.5, solution pH played a minor role for chromium leaching at 25°C. No statistically significant difference was observed due to type of chelator, presence of antioxidant, or surfactant. In order to optimize a biotherapeutic formulation to achieve a target drug product shelf life with acceptable quality, each formulation component must be evaluated for its impact.

Simultaneous determination of Ca, Cu, Ni, Zn and Cd binding strengths with fulvic acid fractions by Schubert's method

USGS Publications Warehouse

Brown, G.K.; MacCarthy, P.; Leenheer, J.A.

1999-01-01

The equilibrium binding of Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ with unfractionated Suwannee river fulvic acid (SRFA) and an enhanced metal binding subfraction of SRFA was measured using Schubert's ion-exchange method at pH 6.0 and at an ionic strength (??) of 0.1 (NaNO3). The fractionation and subfractionation were directed towards obtaining an isolate with an elevated metal binding capacity or binding strength as estimated by Cu2+ potentiometry (ISE). Fractions were obtained by stepwise eluting an XAD-8 column loaded with SRFA with water eluents of pH 1.0 to pH 12.0. Subfractions were obtained by loading the fraction eluted from XAD-8 at pH 5.0 onto a silica gel column and eluting with solvents of increasing polarity. Schuberts ion exchange method was rigorously tested by measuring simultaneously the conditional stability constants (K) of citric acid complexed with the five metals at pH 3.5 and 6.0. The logK of SRFA with Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ determined simultaneously at pH 6.0 follow the sequence of Cu2+>Cd2+>Ni2+>Zn2+>Ca2+ while all logK values increased for the enhanced metal binding subfraction and followed a different sequence of Cu2+>Cd2+>Ca2+>Ni2+>Zn2+. Both fulvic acid samples and citric acid exhibited a 1:1 metal to ligand stochiometry under the relatively low metal loading conditions used here. Quantitative 13C nuclear magnetic resonance spectroscopy showed increases in aromaticity and ketone content and decreases in aliphatic carbon for the elevated metal binding fraction while the carboxyl carbon, and elemental nitrogen, phosphorus, and sulfur content did not change. The more polar, elevated metal binding fraction did show a significant increase in molecular weight over the unfractionated SRFA. Copyright (C) 1999 Elsevier Science B.V.

Adsorption by and artificial release of zinc and lead from porous concrete for recycling of adsorbed zinc and lead and of porous concrete to reduce urban non-point heavy metal runoff.

PubMed

Harada, Shigeki; Yanbe, Miyu

2018-04-01

This report describes the use of porous concrete at the bottom of a sewage trap to prevent runoff of non-point heavy metals into receiving waters, and, secondarily, to reduce total runoff volume during heavy rains in urbanized areas while simultaneously increasing the recharge volume of heavy-metal-free water into underground aquifers. This idea has the advantage of preventing clogging, which is fundamentally very important when using pervious materials. During actual field experiments, two important parameters were identified: maximum adsorption weight of lead and zinc by the volume of porous concrete, and heavy metal recovery rate by artificial acidification after adsorption. To understand the effect of ambient heavy metal concentration, a simple mixing system was used to adjust the concentrations of lead and zinc solutions. The concrete blocks used had been prepared for a previous study by Harada & Komuro (2010). The results showed that maximum adsorption depended on the ambient concentration, expressed as the linear isothermal theory, and that recovery depended on the final pH value (0.5 or 0.0). The dependence on pH is very important for recycling the porous concrete. A pH of 0.5 is important for recycling both heavy metals, especially zinc, (8.0-22.1% of lead and 42-74% of zinc) and porous concrete because porous concrete has not been heavily damaged by acid. However, at a pH of 0.0, the heavy metals could be recovered: 30-60% of the lead and 75-125% of the zinc. At a higher pH, such as 2.0, no release of heavy metals occurred, indicating the safety to the environment of using porous concrete, because the lowest recorded pH of rainfall in Japan is. 4.0. Copyright © 2018 Elsevier Ltd. All rights reserved.

The effect of heavy metal concentration and soil pH on the abundance of selected microbial groups within ArcelorMittal Poland steelworks in Cracow.

PubMed

Lenart, Anna; Wolny-Koładka, Katarzyna

2013-01-01

The present study aimed to identify the effect of heavy metal concentration and soil pH on the abundance of the selected soil microorganisms within ArcelorMittal Poland steelworks, Cracow. The analysis included 20 soil samples, where the concentration of Fe, Zn, Cd, Pb, Ni, Cu, Mn, Cr and soil pH were evaluated together with the number of mesophilic bacteria, fungi, Actinomycetes and Azotobacter spp. In the majority of samples soil pH was alkaline. The limits of heavy metals exceeded in eight samples and in one sample, the concentration of Zn exceeded 31-fold. Chromium was the element which most significantly limited the number of bacteria and Actinomycetes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bae, Wookeun; Shin, Eung Bai; Lee, Kil Chul

The potential hazard of landfill wastes was previously evaluated by examining the extraction procedures for individual waste, although various wastes were co-disposed of in actual landfills. This paper investigates the reduction of extraction-procedure toxicity by co-disposing various combinations of two wastes. When two wastes are mixed homogeneously, the extraction of heavy metals from the waste mixture is critically affected by the extract pH. Thus, co-disposal wastes will have a resultant pH between the pH values of its constituent. The lower the resultant pH, the lower the concentrations of heavy metals in the extract. When these wastes are extracted sequentially, themore » latter extracted waste has a stronger influence on the final concentration of heavy metals in the extract. Small-scale lysimeter experiments confirm that when heavy-metal-bearing leachates Generated from hazardous-waste lysimeters are passed through a nonhazardous-waste lysimeter filled with compost, briquette ash, or refuse-incineration ashes, the heavy-metal concentration in the final leachates decreases significantly. Thus, the heavy-metal leaching could be attenuated if a less extraction-procedure-toxic waste were placed at the bottom of a landfill. 3 refs., 4 figs., 5 tabs.« less

Simulation of CO₂ leakages during injection and storage in sub-seabed geological formations: metal mobilization and biota effects.

PubMed

Rodríguez-Romero, Araceli; Basallote, M Dolores; De Orte, Manoela R; DelValls, T Ángel; Riba, Inmaculada; Blasco, Julián

2014-07-01

To assess the potential effects on metal mobilization due to leakages of CO2 during its injection and storage in marine systems, an experimental set-up was devised and operated, using the polychaete Hediste diversicolor as the model organism. The objective was to study the effects of such leakage in the expected scenarios of pH values between 8.0 and 6.0. Polychaetes were exposed for 10 days to seawater with sediment samples collected in two different coastal areas, one with relatively uncontaminated sediment as reference (RSP) and the other with known contaminated sediment (ML), under pre-determined pH conditions. Survival and metal accumulation (Al, Fe, Mn, Cu, Zn, As and Hg) in the whole body of H. diversicolor were employed as endpoints. Mortality was significant at the lowest pH level in the sediment with highest metal concentrations. In general, metal concentrations in tissues of individuals exposed to the contaminated sediment were influenced by pH. These results indicate that ocean acidification due to CO2 leakages would provoke increased metal mobilization, causing adverse side effects in sediment toxicity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of sulfate reducing bacteria isolated from urban soil

NASA Astrophysics Data System (ADS)

Zhang, Mingliang; Wang, Haixia

2017-05-01

Sulfate reducing bacteria (SRB) was isolated from urban soil and applied for the remediation of heavy metals pollution from acid mine drainage. The morphology and physiological characteristics (e.g. pH and heavy metals tolerance) of SRB was investigated. The SRB was gram-negative bacteria, long rod with slight curve, cell size 0.5× (1.5-2.0) μm. The pH of medium had significant effect on SRB growth and the efficiency of sulfate reduction, and it showed that the suitable pH range was 5-9 and SRB could not survive at pH less than 4. The maximum tolerance of Fe (II), Zn (II), Cd (II), and Cu (II) under acidic condition (pH 5.0) was about 600 mg/L, 150 mg/L, 25 mg/L and 25 mg/L, respectively. The result indicated that SRB isolated in this study could be used for the bioremediation of acid mine drainage (pH>4) within the heavy metals concentrations tolerance.

Mechanisms of intragastric pH sensing.

PubMed

Goo, Tyralee; Akiba, Yasutada; Kaunitz, Jonathan D

2010-12-01

Luminal amino acids and lack of luminal acidity as a result of acid neutralization by intragastric foodstuffs are powerful signals for acid secretion. Although the hormonal and neural pathways underlying this regulatory mechanism are well understood, the nature of the gastric luminal pH sensor has been enigmatic. In clinical studies, high pH, tryptic peptides, and luminal divalent metals (Ca(2+) and Mg(2+)) increase gastrin release and acid production. The calcium-sensing receptor (CaSR), first described in the parathyroid gland but expressed on gastric G cells, is a logical candidate for the gastric acid sensor. Because CaSR ligands include amino acids and divalent metals, and because extracellular pH affects ligand binding in the pH range of the gastric content, its pH, metal, and nutrient-sensing functions are consistent with physiologic observations. The CaSR is thus an attractive candidate for the gastric luminal sensor that is part of the neuroendocrine negative regulatory loop for acid secretion.

Diverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors† †Electronic supplementary information (ESI) available: Experimental and calculation details, and crystallographic information for 2, 3, 4, 6, 8. CCDC 1038665, 1038666, 1038667, 1011534, and 1011533. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00404g Click here for additional data file. Click here for additional data file.

PubMed Central

Kong, Lingbing; Ganguly, Rakesh; Li, Yongxin

2015-01-01

The reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) 1 towards metal precursors and its coordination chemistry were comprehensively studied. While the boron center in 1 is reluctant to coordinate to the alkali metals in their trifluoromethanesulfonate salts (MOTf) (M = Li, Na, K), the unprecedented compound 2 containing two L2PhB: units linked by a cyclic Li(OTf)2Li spacer was obtained from the reaction of 1 with LiOTf. Treatment of 1 with group 9 metal complexes [MCl(COD)]2 (M = Rh, Ir) afforded the first zwitterionic rhodium(i)–boronium complex 3 and the iridium(iii)–borane complex 4, respectively. The reaction pathway may involve C–H activation followed by proton migration from the metals to the boron center, demonstrating the first example of the deprotonation of metal hydrides by a basic boron. In the reactions with coinage metals, 1 could act as a two-electron reducing agent towards the metal chlorides MCl (M = Cu, Ag, Au). Meanwhile, the reaction of 1 with gold chloride supported by a N-heterocyclic carbene (NHC) produced a heteroleptic cationic gold complex [(L2PhB)Au(NHC)]Cl (6) featuring both carbene and L2PhB: ligands on the gold atom. In contrast, an isolable gold chloride complex (L2PhB)AuCl (8) was obtained by direct complexation between 1 and triphenylphosphine-gold chloride via ligand exchange. X-ray diffraction analysis and computational studies revealed the nature of the B:→Au bonding interaction in complexes 6 and 8. Natural Population Analysis (NPA) and Natural Bond Orbital (NBO) analysis support the strong σ-donating property of the L2PhB: ligand. Moreover, preliminary studies showed that complex 8 can serve as an efficient precatalyst for the addition of X–H (X = N, O, C) to alkynes under ambient conditions, demonstrating the first application of a metal complex featuring a neutral boron-based ligand in catalysis. PMID:29308167

Effect of heavy metals on pH buffering capacity and solubility of Ca, Mg, K, and P in non-spiked and heavy metal-spiked soils.

PubMed

Najafi, Sarvenaz; Jalali, Mohsen

2016-06-01

In many parts of the world, soil acidification and heavy metal contamination has become a serious concern due to the adverse effects on chemical properties of soil and crop yield. The aim of this study was to investigate the effect of pH (in the range of 1 to 3 units above and below the native pH of soils) on calcium (Ca), magnesium (Mg), potassium (K), and phosphorus (P) solubility in non-spiked and heavy metal-spiked soil samples. Spiked samples were prepared by cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn) as chloride salts and incubating soils for 40 days. The pH buffering capacity (pHBC) of each sample was determined by plotting the amount of H(+) or OH(-) added (mmol kg(-1)) versus the related pH value. The pHBC of soils ranged from 47.1 to 1302.5 mmol kg(-1) for non-spiked samples and from 45.0 to 1187.4 mmol kg(-1) for spiked soil samples. The pHBC values were higher in soil 2 (non-spiked and spiked) which had higher calcium carbonate content. The results indicated the presence of heavy metals in soils generally decreased the solution pH and pHBC values in spiked samples. In general, solubility of Ca, Mg, and K decreased with increasing equilibrium pH of non-spiked and spiked soil samples. In the case of P, increasing the pH to about 7, decreased the solubility in all soils but further increase of pH from 7, enhanced P solubility. The solubility trends and values for Ca, Mg, and K did not differed significantly in non-spiked and spiked samples. But in the case of P, a reduction in solubility was observed in heavy metal-spiked soils. The information obtained in this study can be useful to make better estimation of the effects of soil pollutants on anion and cation solubility from agricultural and environmental viewpoints.

Hydrothermal carbonization of sewage sludge: The effect of feed-water pH on fate and risk of heavy metals in hydrochars.

PubMed

Zhai, Yunbo; Liu, Xiangmin; Zhu, Yun; Peng, Chuan; Wang, Tengfei; Zhu, Luo; Li, Caiting; Zeng, Guangming

2016-10-01

In this study, the effect of feed-water pH (pH=2-12) on fate and risk of heavy metals (HMs) in hydrochars (HCs) was investigated. Hydrothermal carbonization (HTC) of sewage sludge (SS) was carried out with different feed-water pH at 270°C. The research results showed that changing feed-water pH had a positive effect on accumulating Pb, Ni, Cd and Zn in HCs. Chemical forms of Cu and Cr converted from an unstable state to stable in the alkaline environment while in the acidic condition was opposite. The effect of feed-water pH on the chemical forms of HMs was variable but not significant. Risk assessments of Igeo, Er(i), RAC and RI were applied to evaluate the accumulation levels of individual metal, the potential ecological risks, the bio-availabilities and the comprehensive toxicity and sensitivity of HMs, respectively. The lowest pollution level of HMs was obtained at 270°C with pH=11. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enterobacter asburiae KUNi5, a Nickel Resistant Bacterium for Possible Bioremediation of Nickel Contaminated Sites.

PubMed

Paul, Anirudha; Mukherjee, Samir Kumar

2016-01-01

Nickel resistant bacterial strain Enterobacter asburiae KUNi5 was isolated and showed resistance up to 15 mM and could remove Ni optimally better at 37 degrees C and pH 7. Maximum removal was found at initial concentration of 0.5 to 2 mM, however, growth and Ni removal were affected by other heavy metals. Major amount of the metal was accumulated in the membrane fractions and certain negatively charged groups were found responsible for Ni binding. KUNi5 could also produce 1-aminocyclopropane-1-carboxylate deaminase, indole-acetic acid and siderophore. It seems that KUNi5 could be a possible candidate for Ni detoxification and plant growth promotion in Ni-contaminated field.

Synthesis of poly(aminopropyl/methyl)silsesquioxane particles as effective Cu(II) and Pb(II) adsorbents.

PubMed

Lu, Xin; Yin, Qiangfeng; Xin, Zhong; Li, Yang; Han, Ting

2011-11-30

Poly(aminopropyl/methyl)silsesquioxane (PAMSQ) particles have been synthesized by a one-step hydrolytic co-condensation process using 3-aminopropyltriethoxysilane (APTES) and methyltrimethoxysilane (MTMS) as precursors in the presence of base catalyst in aqueous medium. The amino functionalities of the particles could be controlled by adjusting the organosilanes feed ratio. The compositions of the amino-functionalized polysilsesquioxanes were confirmed by FT-IR spectroscopy, solid-state (29)Si NMR spectroscopy, and elemental analysis. The strong adsorbability of Cu(II) and Pb(II) ions onto PAMSQ particles was systematically examined. The effect of adsorption time, initial metal ions concentration and pH of solutions was studied to optimize the metal ions adsorbability of PAMSQ particles. The kinetic studies indicated that the adsorption process well fits the pseudo-second-order kinetics. Adsorption phenomena appeared to follow Langmuir isotherm. The PAMSQ particles demonstrate the highest Cu(II) and Pb(II) adsorption capacity of 2.29 mmol/g and 1.31 mmol/g at an initial metal ions concentration of 20mM, respectively. The PAMSQ particles demonstrate a promising application in the removal of Cu(II) and Pb(II) ions from aqueous solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

Adsorption of Hg2+, Cu2+ and Zn2+ ions from aqueous solution using formaldehyde cross-linked modified chitosan-thioglyceraldehyde Schiff's base.

PubMed

Monier, M

2012-04-01

A chitosan-thioglyceraldehyde Schiff's base cross-linked magnetic resin (CSTG) was prepared and characterized using various instrumental methods. Then, the prepared resin was used for comparative studies on the removal of toxic metal ions like: Hg(2+), Cu(2+) and Zn(2+) from aqueous solutions. The effects of the initial pH value of the solution, contact time, the initial metal ion concentration and temperature on the adsorption capacity of the composite were investigated. The kinetics data were analyzed by pseudo-first order and pseudo-second order equations. The adsorption kinetics was well described by the pseudo-second order equation, and the adsorption isotherms were better fitted by the Langmuir equation. The maximum theoretical adsorption capacities of the CSTG resin for Hg(2+), Cu(2+) and Zn(2+) were found to be 98±2, 76±1 and 52±1 mg g(-1), respectively. The negative values of Gibbs free energy of adsorption (ΔG(ads°) indicated the spontaneity of the adsorption of all metal ions on the novel resin. Copyright © 2011 Elsevier B.V. All rights reserved.

Pb and Cd binding to natural freshwater biofilms developed at different pH: the important role of culture pH.

PubMed

Hua, Xiuyi; Dong, Deming; Ding, Xiaoou; Yang, Fan; Jiang, Xu; Guo, Zhiyong

2013-01-01

The effects of solution pH on adsorption of trace metals to different types of natural aquatic solid materials have been studied extensively, but few studies have been carried out to investigate the effect of pH at which the solid materials were formed on the adsorption. The purpose of present study is to examine this effect of culture pH on metal adsorption to natural freshwater biofilms. The adsorption of Pb and Cd to biofilms which were developed at different culture pH values (ranging from 6.5 to 9.0) was measured at the same adsorption pH value (6.5). The culture pH had considerable effects on both composition and metal adsorption ability of the biofilms. Higher culture pH usually promoted the accumulation of organic material and Fe oxides in the biofilms. The culture pH also affected the quantity and species of algae in the biofilms. The adsorption of Pb and Cd to the biofilms generally increased with the increase of culture pH. This increase was minor at lower pH range and significant at higher pH range and was more remarkable for Cd adsorption than for Pb adsorption. The notable contribution of organic material to the adsorption at higher culture pH values was also observed. The profound impacts of culture pH on adsorption behavior of biofilms mainly resulted from the variation of total contents of the biofilm components and were also affected by the alteration of composition and properties of the components.

Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor.

PubMed

Pavlović, Jelena; Stopić, Srećko; Friedrich, Bernd; Kamberović, Zeljko

2007-11-01

This paper is a part of the research work on 'Integrated treatment of industrial wastes towards prevention of regional water resources contamination - INTREAT' the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm3, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify. efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. Consumption of NaOH in reactors was 370 cm3, 40 cm3 and 80 cm3, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6 degrees C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm3 at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm3 and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm3 at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6 degrees C. This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes.

Ethanol mediated As(III) adsorption onto Zn-loaded pinecone biochar: Experimental investigation, modeling, and optimization using hybrid artificial neural network-genetic algorithm approach.

PubMed

Zafar, Mohd; Van Vinh, N; Behera, Shishir Kumar; Park, Hung-Suck

2017-04-01

Organic matters (OMs) and their oxidization products often influence the fate and transport of heavy metals in the subsurface aqueous systems through interaction with the mineral surfaces. This study investigates the ethanol (EtOH)-mediated As(III) adsorption onto Zn-loaded pinecone (PC) biochar through batch experiments conducted under Box-Behnken design. The effect of EtOH on As(III) adsorption mechanism was quantitatively elucidated by fitting the experimental data using artificial neural network and quadratic modeling approaches. The quadratic model could describe the limiting nature of EtOH and pH on As(III) adsorption, whereas neural network revealed the stronger influence of EtOH (64.5%) followed by pH (20.75%) and As(III) concentration (14.75%) on the adsorption phenomena. Besides, the interaction among process variables indicated that EtOH enhances As(III) adsorption over a pH range of 2 to 7, possibly due to facilitation of ligand-metal(Zn) binding complexation mechanism. Eventually, hybrid response surface model-genetic algorithm (RSM-GA) approach predicted a better optimal solution than RSM, i.e., the adsorptive removal of As(III) (10.47μg/g) is facilitated at 30.22mg C/L of EtOH with initial As(III) concentration of 196.77μg/L at pH5.8. The implication of this investigation might help in understanding the application of biochar for removal of various As(III) species in the presence of OM. Copyright © 2016. Published by Elsevier B.V.

Pollution in acid mine drainage from mine tailings in Svalbard Norwegian Arctic

NASA Astrophysics Data System (ADS)

Holm, E. B.; Brandvik, P. J.; Steinnes, E.

2003-05-01

Throughout the summer season of 2000 samples of acid mine drainage (AMD) were collected from areas below tailing deposits from the coal mining in Svalbard, Norwegian Arctic. The water was analysed for pH, oxygen, conductivity, 9 sulfate and various metals. Oxygen, pH and conductivity were measured by standard electrodes, sulphate was determined gravimetrically and metals were determined by flame/graphite furnace AAS. The AMD was found to contain heavy metals and sulphate in high concentrations, causing damage to the local tundra vegetation. Large spatial variation however was observed in pH (2.5-9.5) as well as in metal concentrations in the AMD, indicating strongly inhomogeneous distribution of sulphide minerais in the tailing deposits.

Process for removing metals from water

DOEpatents

Napier, John M.; Hancher, Charles M.; Hackett, Gail D.

1989-01-01

A process for removing metals from water including the steps of prefiltering solids from the water, adjusting the pH to between about 2 and 3, reducing the amount of dissolved oxygen in the water, increasing the pH to between about 6 and 8, adding water-soluble sulfide to precipitate insoluble sulfide- and hydroxide-forming metals, adding a flocculating agent, separating precipitate-containing floc, and postfiltering the resultant solution. The postfiltered solution may optionally be eluted through an ion exchange resin to remove residual metal ions.

Process for removing metals from water

DOEpatents

Napier, J.M.; Hancher, C.M.; Hackett, G.D.

1987-06-29

A process for removing metals from water including the steps of prefiltering solids from the water, adjusting the pH to between about 2 and 3, reducing the amount of dissolved oxygen in the water, increasing the pH to between about 6 and 8, adding water-soluble sulfide to precipitate insoluble sulfide- and hydroxide-forming metals, adding a containing floc, and postfiltering the resultant solution. The postfiltered solution may optionally be eluted through an ion exchange resin to remove residual metal ions. 2 tabs.

Biosorption of Cr(VI) by Ceratocystis paradoxa MSR2 Using Isotherm Modelling, Kinetic Study and Optimization of Batch Parameters Using Response Surface Methodology

PubMed Central

Ramalingam, Chidambaram

2015-01-01

This study is focused on the possible use of Ceratocystis paradoxa MSR2 native biomass for Cr(VI) biosorption. The influence of experimental parameters such as initial pH, temperature, biomass dosage, initial Cr(VI) concentration and contact time were optimized using batch systems as well as response surface methodology (RSM). Maximum Cr(VI) removal of 68.72% was achieved, at an optimal condition of biomass dosage 2g L−1, initial Cr(VI) concentration of 62.5 mg L−1 and contact time of 60 min. The closeness of the experimental and the predicted values exhibit the success of RSM. The biosorption mechanism of MSR2 biosorbent was well described by Langmuir isotherm and a pseudo second order kinetic model, with a high regression coefficient. The thermodynamic study also revealed the spontaneity and exothermic nature of the process. The surface characterization using FT-IR analysis revealed the involvement of amine, carbonyl and carboxyl groups in the biosorption process. Additionally, desorption efficiency of 92% was found with 0.1 M HNO3. The Cr(VI) removal efficiency, increased with increase in metal ion concentration, biomass concentration, temperature but with a decrease in pH. The size of the MSR2 biosorbent material was found to be 80 μm using particle size analyzer. Atomic force microscopy (AFM) visualizes the distribution of Cr(VI) on the biosorbent binding sites with alterations in the MSR2 surface structure. The SEM-EDAX analysis was also used to evaluate the binding characteristics of MSR2 strain with Cr(VI) metals. The mechanism of Cr(VI) removal of MSR2 biomass has also been proposed. PMID:25822726

Bacterial exopolysaccharides as a modern biotechnological tool for modification of fungal laccase properties and metal ion binding.

PubMed

Osińska-Jaroszuk, Monika; Jaszek, Magdalena; Starosielec, Magdalena; Sulej, Justyna; Matuszewska, Anna; Janczarek, Monika; Bancerz, Renata; Wydrych, Jerzy; Wiater, Adrian; Jarosz-Wilkołazka, Anna

2018-03-26

Four bacterial EPSs extracted from Rhizobium leguminosarum bv. trifolii Rt24.2, Sinorhizobium meliloti Rm1021, Bradyrhizobium japonicum USDA110, and Bradyrhizobium elkanii USDA76 were determined towards their metal ion adsorption properties and possible modification of Cerrena unicolor laccase properties. The highest magnesium and iron ion-sorption capacity (~ 42 and ~ 14.5%, respectively) was observed for EPS isolated from B. japonicum USDA110. An evident influence of EPSs on the stability of laccase compared to the control values (without EPSs) was shown after 30-day incubation at 25 °C. The residual activity of laccases was obtained in the presence of Rh76EPS and Rh1021EPS, i.e., 49.5 and 41.5% of the initial catalytic activity, respectively. This result was confirmed by native PAGE electrophoresis. The EPS effect on laccase stability at different pH (from 3.8 to 7.0) was also estimated. The most significant changes at the optimum pH value (pH 5.8) was observed in samples of laccase stabilized by Rh76EPS and Rh1021EPS. Cyclic voltamperometry was used for analysis of electrochemical parameters of laccase stabilized by bacterial EPS and immobilized on single-walled carbon nanotubes (SWCNTs) with aryl residues. Laccases with Rh76EPS and Rh1021EPS had an evident shift of the value of the redox potential compared to the control without EPS addition. In conclusion, the results obtained in this work present a new potential use of bacterial EPSs as a metal-binding component and a modulator of laccase properties especially stability of enzyme activity, which can be a very effective tool in biotechnology and industrial applications.

Irrigation water quality influences heavy metal uptake by willows in biosolids.

PubMed

Laidlaw, W Scott; Baker, Alan J M; Gregory, David; Arndt, Stefan K

2015-05-15

Phytoextraction is an effective method to remediate heavy metal contaminated landscapes but is often applied for single metal contaminants. Plants used for phytoextraction may not always be able to grow in drier environments without irrigation. This study investigated if willows (Salix x reichardtii A. Kerner) can be used for phytoextraction of multiple metals in biosolids, an end-product of the wastewater treatment process, and if irrigation with reclaimed and freshwater influences the extraction process. A plantation of willows was established directly onto a tilled stockpile of metal-contaminated biosolids and irrigated with slightly saline reclaimed water (EC ∼2 dS/cm) at a wastewater processing plant in Victoria, Australia. Biomass was harvested annually and analysed for heavy metal content. Phytoextraction of cadmium, copper, nickel and zinc was benchmarked against freshwater irrigated willows. The minimum irrigation rate of 700 mm per growing season was sufficient for willows to grow and extract metals. Increasing irrigation rates produced no differences in total biomass and also no differences in the extraction of heavy metals. The reclaimed water reduced both the salinity and the acidity of the biosolids significantly within the first 12 months after irrigation commenced and after three seasons the salinity of the biosolids had dropped to <15% of initial values. A flushing treatment to remove excess salts was therefore not necessary. Irrigation had an impact on biosolids attributes such as salinity and pH, and that this had an influence on metal extraction. Reclaimed water irrigation reduced the biosolid pH and this was associated with reductions of the extraction of Ni and Zn, it did not influence the extraction of Cu and enhanced the phytoextraction of Cd, which was probably related to the high chloride content of the reclaimed water. Our results demonstrate that flood-irrigation with reclaimed water was a successful treatment to grow willows in a dry climate. However, the reclaimed water can also change biosolids properties, which will influence the effectiveness of willows to extract different metals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interactions of Hydrazine and of Hydrazine Derivatives with Soil Constituents and with Soils.

DTIC Science & Technology

1982-01-31

exchangeable metal cations held by the clay and humic colloids, or the metal of the hydrous oxide colloids. The pH values of the natural soil solution of most...hydrazine into a soil system will tend to increase the pH of the soil solution . Hydrous oxides of iron and aluminium are insoluble at high pH, and these...aeration, and by the soil solution pH. Treatment of contaminated soils can alter these properties in order to promote the degradation or immobilization of

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Recovery Of Chromium Metal (VI) Using Supported Liquid Membrane (SLM) Method, A study of Influence of NaCl and pH in Receiving Phase on Transport

NASA Astrophysics Data System (ADS)

Cholid Djunaidi, Muhammad; Lusiana, Retno A.; Rahayu, Maya D.

2017-06-01

Chromium metal(VI) is a valuable metal but in contrary has high toxicity, so the separation and recovery from waste are very important. One method that can be used for the separation and recovery of chromium (VI) is a Supported Liquid Membrane (SLM). SLM system contains of three main components: a supporting membrane, organic solvents and carrier compounds. The supported Membrane used in this research is Polytetrafluoroethylene (PTFE), organic solvent is kerosene, and the carrier compound used is aliquat 336. The supported liquid membrane is placed between two phases, namely, feed phase as the source of analyte (Cr(VI)) and the receiving phase as the result of separation. Feed phase is the electroplating waste which contains of chromium metal with pH variation about 4, 6 and 9. Whereas the receiving phase are the solution of HCl, NaOH, HCl-NaCl and NaOH-NaCl with pH variation about 1, 3, 5 and 7. The efficiency separation is determined by measurement of chromium in the feed and the receiving phase using AAS (Atomic Absorption Spectrophotometry). The experiment results show that transport of Chrom (VI) by Supported Liquid membrane (SLM) is influenced by pH solution in feed phase and receiving phase as well as NaCl in receiving phase. The highest chromium metal is transported from feed phase about 97,78%, whereas in receiving phase shows about 58,09%. The highest chromium metal transport happens on pH 6 in feed phase, pH 7 in receiving phase with the mixture of NaOH and NaCl using carrier compound aliquat 336.

Adsorptive removal of heavy metals from water using sodium titanate nanofibres loaded onto GAC in fixed-bed columns.

PubMed

Sounthararajah, D P; Loganathan, P; Kandasamy, J; Vigneswaran, S

2015-04-28

Heavy metals are serious pollutants in aquatic environments. A study was undertaken to remove Cu, Cd, Ni, Pb and Zn individually (single metal system) and together (mixed metals system) from water by adsorption onto a sodium titanate nanofibrous material. Langmuir adsorption capacities (mg/g) at 10(-3)M NaNO3 ionic strength in the single metal system were 60, 83, 115 and 149 for Ni, Zn, Cu, and Cd, respectively, at pH 6.5 and 250 for Pb at pH 4.0. In the mixed metals system they decreased at high metals concentrations. In column experiments with 4% titanate material and 96% granular activated carbon (w/w) mixture at pH 5.0, the metals breakthrough times and adsorption capacities (for both single and mixed metals systems) decreased in the order Pb>Cd, Cu>Zn>Ni within 266 bed volumes. The amounts adsorbed were up to 82 times higher depending on the metal in the granular activated carbon+titanate column than in the granular activated carbon column. The study showed that the titanate material has high potential for removing heavy metals from polluted water when used with granular activated carbon at a very low proportion in fixed-bed columns. Copyright © 2015 Elsevier B.V. All rights reserved.

Engineering the metal sensitive sites in Macrolampis sp2 firefly luciferase and use as a novel bioluminescent ratiometric biosensor for heavy metals.

PubMed

Gabriel, Gabriele V M; Viviani, Vadim R

2016-12-01

Most luminescent biosensors for heavy metals are fluorescent and rely on intensity measurements, whereas a few are ratiometric and rely on spectral changes. Bioluminescent biosensors for heavy metals are less common. Firefly luciferases have been coupled to responsive promoters for mercury and arsenium, and used as light on biosensors. Firefly luciferase bioluminescence spectrum is naturally sensitive to heavy metal cations such as zinc and mercury and to pH. Although pH sensitivity of firefly luciferases was shown to be useful for ratiometric estimation of intracellular pH, its potential use for ratiometric estimation of heavy metals was never considered. Using the yellow-emitting Macrolampis sp2 firefly luciferase and site-directed mutagenesis, we show that the residues H310 and E354 constitute two critical sites for metal sensitivity that can be engineered to increase sensitivity to zinc, nickel, and mercury. A linear relationship between cation concentration and the ratio of bioluminescence intensities at 550 and 610 nm allowed, for the first time, the ratiometric estimation of heavy metals concentrations down to 0.10 mM, demonstrating the potential applicability of firefly luciferases as enzymatic and intracellular ratiometric metal biosensors.

Sorption and desorption of Pb(II) to biochar as affected by oxidation and pH.

PubMed

Wang, Qian; Wang, Bing; Lee, Xinqing; Lehmann, Johannes; Gao, Bin

2018-09-01

The use of biochar for the removal of heavy metals from water has environmental benefits. In order to elucidate the potential application of highly functionalized biochar for the removal of Pb(II) in aqueous solution, maple wood biochar was oxidized using hydrogen peroxide. The pH values of oxidized biochar ranged from 8.1 to 3.7, with one set being adjusted to a pH of 7 as a comparison. It was found that oxidizing the biochars increased their Pb(II) adsorption capacity if the pH remained below 6 (strong oxidation), but decreased their Pb(II) adsorption ability above pH6 (weak oxidation). After adjusting the pH of oxidized biochar to pH7, the Pb(II) adsorption capacity further increased two to sixfold for oxidized biochars originally at pH3.7-6. The adsorption characteristics of Pb(II) were well described by the Langmuir equation. Adsorption of Pb(II) was not fully reversible in water. Less than 6% of Pb(II) desorbed in water in two consecutive steps than was previously adsorbed, for biochars with a pH below 7, irrespective of oxidation. Recovery using an extraction with 0.1M NaNO 3 increased from 0.7% to 32.7% of Pb(II) undesorbed by both preceding water extractions with increasing oxidation, for biochars with a pH below 7. Unextractable Pb(II) was lower at low oxidation but increased to 99.0% of initially adsorbed amounts at low pH, which indicated that the adsorption of Pb(II) on oxidized biochar is pH independent. Copyright © 2018 Elsevier B.V. All rights reserved.

A Comparative Analysis of the Corrosive Effect of Artificial Saliva of Variable pH on DMLS and Cast Co-Cr-Mo Dental Alloy

PubMed Central

Puskar, Tatjana; Jevremovic, Danimir; Williams, Robert J.; Eggbeer, Dominic; Vukelic, Djordje; Budak, Igor

2014-01-01

Dental alloys for direct metal laser sintering (DMLS) are available on the market today, but there is little scientific evidence reported on their characteristics. One of them is the release of ions, as an indicator of the corrosion characteristics of a dental alloy. Within this research, the difference in the elution of metals from DMLS and cast (CM) samples of Co-Cr-Mo dental alloy in saliva-like medium of three different pH was examined by inductively-coupled plasma mass spectrometry (ICP-MS). The obtained results show that the metal elution in artificial saliva from the DMLS alloy was lower than the elution from the CM alloy. The release of all investigated metal ions was influenced by the acidity, both from the DMLS and CM alloy, throughout the investigated period of 30 days. The change in acidity from a pH of 6.8 to a pH of 2.3 for the cast alloy led to a higher increase of the elution of Co, Cr and Mo from CM than from the DMLS alloy. The greatest release out of Co, Cr and Mo was for Co for both tested alloys. Further, the greatest release of all ions was measured at pH 2.3. In saliva of pH 2.3 and pH 4.5, the longer the investigated period, the higher the difference between the total metal ion release from the CM and DMLS alloys. Both alloys showed a safe level of elution according to the ISO definition in all investigated acidic environments. PMID:28788197

A Comparative Analysis of the Corrosive Effect of Artificial Saliva of Variable pH on DMLS and Cast Co-Cr-Mo Dental Alloy.

PubMed

Puskar, Tatjana; Jevremovic, Danimir; Williams, Robert J; Eggbeer, Dominic; Vukelic, Djordje; Budak, Igor

2014-09-11

Dental alloys for direct metal laser sintering (DMLS) are available on the market today, but there is little scientific evidence reported on their characteristics. One of them is the release of ions, as an indicator of the corrosion characteristics of a dental alloy. Within this research, the difference in the elution of metals from DMLS and cast (CM) samples of Co-Cr-Mo dental alloy in saliva-like medium of three different pH was examined by inductively-coupled plasma mass spectrometry (ICP-MS). The obtained results show that the metal elution in artificial saliva from the DMLS alloy was lower than the elution from the CM alloy. The release of all investigated metal ions was influenced by the acidity, both from the DMLS and CM alloy, throughout the investigated period of 30 days. The change in acidity from a pH of 6.8 to a pH of 2.3 for the cast alloy led to a higher increase of the elution of Co, Cr and Mo from CM than from the DMLS alloy. The greatest release out of Co, Cr and Mo was for Co for both tested alloys. Further, the greatest release of all ions was measured at pH 2.3. In saliva of pH 2.3 and pH 4.5, the longer the investigated period, the higher the difference between the total metal ion release from the CM and DMLS alloys. Both alloys showed a safe level of elution according to the ISO definition in all investigated acidic environments.

ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

PubMed Central

Razzell, W. E.; Trussell, P. C.

1963-01-01

Razzell, W. E. (British Columbia Research Council, Vancouver, Canada) and P. C. Trussell. Isolation and properties of an iron-oxidizing Thiobacillus. J. Bacteriol. 85:595–603. 1963. — An organism isolated from acidic copper-leaching waters has been shown to oxidize ferrous ions, sulfur, and metallic sulfides but exhibit peculiar responses to thiosulfate. The name Thiobacillus ferrooxidans has been used to describe it. A pH of 2.5 is optimal for growth on iron, sulfur, and metallic sulfides, but cells free from iron can be obtained from growth at pH 1.6, and sulfur cultures adjusted to pH 5.5 readily attain a pH of 1.8. A stationary cultivation procedure appears superior to percolation techniques for studying the oxidation of finely divided metallic sulfides. Concentrations of soluble copper in excess of 1 g per liter were obtained from chalcopyrite in less than 4 weeks. Chalcocite oxidation proceeded in the absence of iron. Sodium chloride inhibits iron oxidation without preventing oxidation of metallic sulfides by the organism. PMID:14042937

Investigations of Heavy Metal Ion Sorption Using Nanocomposites of Iron-Modified Biochar

NASA Astrophysics Data System (ADS)

Kołodyńska, D.; Bąk, J.; Kozioł, M.; Pylypchuk, L. V.

2017-06-01

Magnetic biochar nanocomposites were obtained by modification of biochar by zero-valent iron. The article provides information on the impact of contact time, initial Cd(II), Co(II), Zn(II), and Pb(II) ion concentrations, dose of the sorbents, solution pH and temperature on the adsorption capacity. On the basis of experiments, it was found that the optimum parameters for the sorption process are phase contact time 360 min (after this time, the equilibrium of all concentrations is reached), the dose of sorbent equal to 5 g/dm3, pH 5 and the temperature 295 K. The values of parameters calculated from the kinetic models and isotherms present the best match to the pseudo second order and Langmuir isotherm models. The calculated thermodynamic parameters ΔH 0, ΔS 0 and ΔG 0 indicate that the sorption of heavy metal ions is an exothermic and spontaneous process as well as favoured at lower temperatures, suggesting the physical character of sorption. The solution of nitric acid(V) at the concentration 0.1 mol/dm3 was the best acidic desorbing agent used for regeneration of metal-loaded magnetic sorbents. The physicochemical properties of synthesized composites were characterized by FTIR, SEM, XRD, XPS and TG analyses. The point characteristics of the double layer for biochar pHPZC and pHIEP were designated.

Inoculation of Brassica oxyrrhina with plant growth promoting bacteria for the improvement of heavy metal phytoremediation under drought conditions.

PubMed

Ma, Ying; Rajkumar, Mani; Zhang, Chang; Freitas, Helena

2016-12-15

The aim of this study was to investigate the effects of drought resistant serpentine rhizobacteria on plant growth and metal uptake by Brassica oxyrrhina under drought stress (DS) condition. Two drought resistant serpentine rhizobacterial strains namely Pseudomonas libanensis TR1 and Pseudomonas reactans Ph3R3 were selected based on their ability to stimulate seedling growth in roll towel assay. Further assessment on plant growth promoting (PGP) parameters revealed their ability to produce indole-3-acetic acid, siderophore and 1-aminocyclopropane-1-carboxylate deaminase. Moreover, both strains exhibited high resistance to various heavy metals, antibiotics, salinity and extreme temperature. Inoculation of TR1 and Ph3R3 significantly increased plant growth, leaf relative water and pigment content of B. oxyrrhina, whereas decreased concentrations of proline and malondialdehyde in leaves under metal stress in the absence and presence of DS. Regardless of soil water conditions, TR1 and Ph3R3 greatly improved organ metal concentrations, translocation and bioconcentration factors of Cu and Zn. The successful colonization and metabolic activities of P. libanensis TR1 and P. reactans Ph3R3 represented positive effects on plant development and metal phytoremediation under DS. These results indicate that these strains could be used as bio-inoculants for the improvement of phytoremediation of metal polluted soils under semiarid conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Carbon-armored Co9S8 nanoparticles as all-pH efficient and durable H2-evolving electrocatalysts.

PubMed

Feng, Liang-Liang; Li, Guo-Dong; Liu, Yipu; Wu, Yuanyuan; Chen, Hui; Wang, Yun; Zou, Yong-Cun; Wang, Dejun; Zou, Xiaoxin

2015-01-14

Splitting water to produce hydrogen requires the development of non-noble-metal catalysts that are able to make this reaction feasible and energy efficient. Herein, we show that cobalt pentlandite (Co9S8) nanoparticles can serve as an electrochemically active, noble-metal-free material toward hydrogen evolution reaction, and they work stably in neutral solution (pH 7) but not in acidic (pH 0) and basic (pH 14) media. We, therefore, further present a carbon-armoring strategy to increase the durability and activity of Co9S8 over a wider pH range. In particular, carbon-armored Co9S8 nanoparticles (Co9S8@C) are prepared by direct thermal treatment of a mixture of cobalt nitrate and trithiocyanuric acid at 700 °C in N2 atmosphere. Trithiocyanuric acid functions as both sulfur and carbon sources in the reaction system. The resulting Co9S8@C material operates well with high activity over a broad pH range, from pH 0 to 14, and gives nearly 100% Faradaic yield during hydrogen evolution reaction under acidic (pH 0), neutral (pH 7), and basic (pH 14) media. To the best of our knowledge, this is the first time that a transition-metal chalcogenide material is shown to have all-pH efficient and durable electrocatalytic activity. Identifying Co9S8 as the catalytically active phase and developing carbon-armoring as the improvement strategy are anticipated to give a fresh impetus to rational design of high-performance noble-metal-free water splitting catalysts.

Performance of calcium peroxide for removal of endocrine-disrupting compounds in waste activated sludge and promotion of sludge solubilization.

PubMed

Zhang, Ai; Wang, Jie; Li, Yongmei

2015-03-15

Removal of six phenolic endocrine disrupting compounds (EDCs) (estrone, 17β-estradiol, 17α-ethinylestradiol, estriol, bisphenol A, and 4-nonylphenols) from waste activated sludge (WAS) was investigated using calcium peroxide (CaO2) oxidation. Effects of initial pH and CaO2 dosage were investigated. The impacts of CaO2 treatment on sludge solubilization and anaerobic digestion were also evaluated. Specifically, the role of reactive oxygen species (ROS) in EDC degradation during CaO2 oxidation was tested. Effects of 6 metal ions contained in the sludge matrix on EDC degradation were also evaluated. The results showed that CaO2 treatment can be a promising technology for EDC removal and facilitating sludge reuse. The EDC removal efficiencies increased with the increase in CaO2 dosage. At CaO2 doses of more than 0.34 g per gram of total solid (g g(-1) TS), more than 50% of EDCs were removed in a wide pH range of 2-12. Higher removal efficiencies were achieved at initial pH values of 12 and 2. The products of EDCs during CaO2 oxidation had less estrogenic activity than the originals. Under the conditions of neutral pH and CaO2 dosage = 0.34 g g(-1) TS, the sludge solubilization can be improved by increasing the soluble total organic carbon (STOC) and volatile suspended solids (VSS) reduction by 25% and 27% in 7 d, respectively; the volatile fatty acid (VFA) production was enhanced by 96% in the 15 d following anaerobic digestion. The ROS released by CaO2 are the main factors contributing to EDC removal, among which, hydroxyl radicals (OH) play the most important role. Metal ions contained in the sludge matrix also affected EDC removal. For most cases, Fe, Cu, and Zn had positive effects; Mn and Ag had negative effects; and Mg had an insignificant effect on EDC removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interaction of Tryptophane and Phenylalanine with Cadmium and Molybdenum Ferrocyanides and Its Implications in Chemical Evolution and Origins of Life.

NASA Astrophysics Data System (ADS)

Tewari, Brij

2016-07-01

Insoluble metal hexacyanoferrate(II) complexes could have concentrated biomonomers from dilute prebiotic soup during course of chemical evolution and origin of life or primitive earth. In the light of above hypothesis, adsorption of tryptophane and phenylalanine was studied on cadmium and molybdenum ferrocyanides at neutral pH (7.0 ± 0.01) and at a temperature of 30 ± 1º C. Interaction of amino acids with metal ferrocyanides are found to be maximum at neutral pH. Neutral pH is chosen for the adsorption studies because most of the reactions in biological systems taken place at neutral pH range. Adsorption trend follow Langmuir isotherm model. The Langmuir constants b and Qo were calculated at neutral pH, tryptophane was found to more adsorbed than phenylalanine on both metal ferrocyanides studied. Molybdenum ferrocyanides studied. Molybdenum ferrocyanides was found to have more uptake capacity for both adsorbates than cadmium ferrocyanides. The present study suggests that metal ferrocyanides might have played a role in the stabilization of biomolecules through their surface activity during course of chemical solution and origins of life on primitive earth.

Batch versus column modes for the adsorption of radioactive metal onto rice husk waste: conditions optimization through response surface methodology.

PubMed

Kausar, Abida; Bhatti, Haq Nawaz; Iqbal, Munawar; Ashraf, Aisha

2017-09-01

Batch and column adsorption modes were compared for the adsorption of U(VI) ions using rice husk waste biomass (RHWB). Response surface methodology was employed for the optimization of process variables, i.e., (pH (A), adsorbent dose (B), initial ion concentration (C)) in batch mode. The B, C and C 2 affected the U(VI) adsorption significantly in batch mode. The developed quadratic model was found to be validated on the basis of regression coefficient as well as analysis of variance. The predicted and actual values were found to be correlated well, with negligible residual value, and B, C and C 2 were significant terms. The column study was performed considering bed height, flow rate and initial metal ion concentration, and adsorption efficiency was evaluated through breakthrough curves and bed depth service time and Thomas models. Adsorption was found to be dependent on bed height and initial U(VI) ion concentration, and flow rate decreased the adsorption capacity. Thomas models fitted well to the U(VI) adsorption onto RHWB. Results revealed that RHWB has potential to remove U(VI) ions and batch adsorption was found to be efficient versus column mode.

THE USEPA'S METAL FINISHING FACILITY RISK SCREENING TOOL (MFFRST)

EPA Science Inventory

The US Environmetal ProtectionAgenccy's Metal Finishing
Facility Risk Screening Tool (MFFRST)

William M. Barrett Jr, Ph.D. , P.E. ; Paul Harten, Ph.D.1, and Matthew Lorber

The US Environmental Protection Agency completed the development of the first version of...

Reuse of acid coagulant-recovered drinking waterworks sludge residual to remove phosphorus from wastewater

NASA Astrophysics Data System (ADS)

Yang, Lan; Wei, Jie; Zhang, Yumei; Wang, Jianli; Wang, Dongtian

2014-06-01

Acid coagulant-recovered drinking waterworks sludge residual (DWSR) is a waste product from drinking waterworks sludge (DWS) treatment with acid for coagulant recovery. In this study, we evaluated DWSR as a potential phosphorus (P) removing material in wastewater treatment by conducting a series of batch and semi-continuous tests. Batch tests were carried out to study the effects of pH, initial concentration, and sludge dose on P removal. Batch test results showed that the P removal efficiency of DWSR was highly dependent on pH. Calcinated DWSR (C-DWSR) performed better in P removal than DWSR due to its higher pH. At an optimum initial pH value of 5-6 and a sludge dose of 10 g/L, the P removal rates of DWSR and DWS decreased from 99% and 93% to 84% and 14%, respectively, and the specific P uptake of DWSR and DWS increased from 0.19 and 0.19 mg P/g to 33.60 and 5.72 mg P/g, respectively, when the initial concentration was increased from 2 to 400 mg/L. The effective minimum sludge doses of DWSR and DWS were 0.5 g/L and 10 g/L, respectively, when the P removal rates of 90% were obtained at an initial concentration of 10 mg/L. Results from semi-continuous test indicated that P removal rates over 99% were quickly achieved for both synthetic and actual wastewater (lake water and domestic sewage). These rates could be maintained over a certain time under a certain operational conditions including sludge dose, feed flow, and initial concentration. The physicochemical properties analysis results showed that the contents of aluminum (Al) and iron (Fe) in DWSR were reduced by 50% and 70%, respectively, compared with DWS. The insoluble Al and Fe hydroxide in DWS converted into soluble Al and Fe in DWSR. Metal leaching test results revealed that little soluble Al and Fe remained in effluent when DWSR was used for P removal. We deduced that chemical precipitation might be the major action for P removal by DWSR and that adsorption played only a marginal role.

Metal separation from mixed types of batteries using selective precipitation and liquid-liquid extraction techniques.

PubMed

Provazi, Kellie; Campos, Beatriz Amaral; Espinosa, Denise Crocce Romano; Tenório, Jorge Alberto Soares

2011-01-01

The purpose of this paper is to study metal separation from a sample composed of a mixture of the main types of spent household batteries, using a hydrometallurgical route, comparing selective precipitation and liquid-liquid extraction separation techniques. The preparation of the solution consisted of: grinding the waste of mixed batteries, reduction and volatile metals elimination using electric furnace and acid leaching. From this solution two different routes were studied: selective precipitation with sodium hydroxide and liquid-liquid extraction using Cyanex 272 [bis(2,4,4-trimethylpentyl) phosphoric acid] as extracting agent. The best results were obtained from liquid-liquid extraction in which Zn had a 99% extraction rate at pH 2.5. More than 95% Fe was extracted at pH 7.0, the same pH at which more than 90% Ce was extracted. About 88% Mn, Cr and Co was extracted at this pH. At pH 3.0, more than 85% Ni was extracted, and at pH 3.5 more than 80% of Cd and La was extracted. Copyright © 2010 Elsevier Ltd. All rights reserved.

Universal Surface-initiated Polymerization of Antifouling Zwitterionic Brushes Using A Mussel-Mimetic Peptide Initiator

PubMed Central

Kuang, Jinghao; Messersmith, Phillip B.

2012-01-01

We report a universal method for the surface-initated polymerization (SIP) of a antifouling polymer brush on various classes of surfaces, including noble metals, metal oxides and inert polymers. Inspired by the versatility of mussel adhesive proteins, we synthesized a novel bifunctional tripeptide bromide (BrYKY) which combines an atom transfer radical polymerization (ATRP) initiating alkyl bromide with l-3,4-dihydroxyphenylalanine (DOPA) and lysine. Simple dip-coating of substrates with variable wetting properties and compositions, including Teflon®, in a BrYKY solution at pH 8.5 led to formation of a thin film of cross-linked BrYKY. Subsequently, we showed that the BrYKY layer initiated the ATRP of a zwitterionic monomer, sulfobetaine methacrylate (SBMA) on all substrates, resulting in high density antifouling pSBMA brushes. Both BrYKY deposition and pSBMA grafting were unambiguously confirmed by ellipsometry, X-ray photoelectron spectroscopy and goniometry. All substrates that were coated with BrYKY/pSBMA dramatically reduced bacterial adhesion for 24 h and also resisted mammalian cell adhesion for at least 4 months, demonstrating the long-term stability of the BrYKY anchoring and antifouling properties of pSBMA. The use of BrYKY as a primer and polymerization initiator has the potential to be widely employed in surface grafted polymer brush modifications for biomedical and other applications. PMID:22506651

Effect of initial pH on anaerobic co-digestion of kitchen waste and cow manure.

PubMed

Zhai, Ningning; Zhang, Tong; Yin, Dongxue; Yang, Gaihe; Wang, Xiaojiao; Ren, Guangxin; Feng, Yongzhong

2015-04-01

This study investigated the effects of different initial pH (6.0, 6.5, 7.0, 7.5 and 8.0) and uncontrolled initial pH (CK) on the lab-scale anaerobic co-digestion of kitchen waste (KW) with cow manure (CM). The variations of pH, alkalinity, volatile fatty acids (VFAs) and total ammonia nitrogen (NH4(+)-N) were analyzed. The modified Gompertz equation was used for selecting the optimal initial pH through comprehensive evaluation of methane production potential, degradation of volatile solids (VS), and lag-phase time. The results showed that CK and the fermentation with initial pH of 6.0 failed. The pH values of the rest treatments reached 7.7-7.9 with significantly increased methane production. The predicted lag-phase times of treatments with initial pH of 6.5 and 7.5 were 21 and 22 days, which were 10 days shorter than the treatments with initial pH of 7.0 and 8.0, respectively. The maximum methane production potential (8579 mL) and VS degradation rate (179.8 mL/g VS) were obtained when the initial pH was 7.5, which is recommended for co-digestion of KW and CM. Copyright © 2015 Elsevier Ltd. All rights reserved.

Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study.

PubMed

Kottalanka, Ravi K; Harinath, A; Rej, Supriya; Panda, Tarun K

2015-12-14

We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very narrow polydispersity index in comparison to that of magnesium complexes 5 and 6.

Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with polyacrylic acid.

PubMed

Montavon, G; Bouby, M; Huclier-Markai, S; Grambow, B; Geckeis, H; Rabung, T; Pashalidis, I; Amekraz, B; Moulin, C

2008-11-15

The trivalent metal ion (M(III)=Cm, Eu)/polyacrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L(-1)-50 g L(-1)) and metal ion concentrations (2x10(-9)-10(-3) M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFlFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(III)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant.

Effect of experimental variables onto Co(2+) and Sr(2+) sorption behavior in red mud-water suspensions.

PubMed

Milenković, Aleksandra S; Smičiklas, Ivana D; Šljivić-Ivanović, Marija Z; Živković, Ljiljana S; Vukelić, Nikola S

2016-07-02

The prospects of rinsed red mud (alumina production residue) utilization for liquid radioactive waste treatment have been investigated, with Co(2+) and Sr(2+) as model cations of radioactive elements. To evaluate the sorption effectiveness and corresponding binding mechanisms, the process was analyzed in batch conditions, by varying experimental conditions (pH, Co(2+) and Sr(2+) concentrations in single solutions and binary mixtures, contact time, and the concentration of competing cations and ligands common in liquid radioactive waste). Comparison of the Co(2+) and Sr(2+) sorption pH edges with the red mud isoelectric point has revealed that Co(2+) removal took place at both positive and negative red mud surface, while Sr(2+) sorption abruptly increased when the surface became negatively charged. The increase of initial cation content and pH resulted in increased equilibrium times and sorption capacity and decreased rate constants. From single metal solutions and various binary mixtures, Co(2+) was sorbed more efficiently and selectively than Sr(2+). While Sr(2+) sorption was reduced by coexisting cations in the order Al(3+) ≥ Ca(2+) >Na(+) ≥Cs(+), removal of Co(2+) was affected by Al(3+) species and complexing agents (EDTA and citrate). Desorption of Co(2+) was negligible in Ca(2+) and Sr(2+) containing media and in solutions with initial pH 4-7. Sr(2+) desorption was generally more pronounced, especially at low pH and in the presence of Co(2+). Collected macroscopic data signify that Co(2+) sorption by red mud minerals occurred via strong chemical bonds, while Sr(2+) was retained mainly by weaker ion-exchange or electrostatic interactions. Results indicate that the rinsed red mud represent an efficient, low-cost sorbent for Co(2+) and Sr(2+) immobilization.

Aminopyridine modified Spirulina platensis biomass for chromium(VI) adsorption in aqueous solution.

PubMed

Bayramoglu, Gulay; Akbulut, Aydin; Arica, M Yakup

Chemical modification of Spirulina platensis biomass was realized by sequential treatment of algal surface with epichlorohydrin and aminopyridine. Adsorptive properties of Cr(VI) ions on native and aminopyridine modified algal biomass were investigated by varying pH, contact time, ionic strength, initial Cr(VI) concentration, and temperature. FTIR and analytical analysis indicated that carboxyl and amino groups were the major functional groups for Cr(VI) ions adsorption. The optimum adsorption was observed at pH 3.0 for native and modified algal biomasses. The adsorption capacity was found to be 79.6 and 158.7 mg g(-1), for native and modified algal biomasses, respectively. For continuous system studies, the experiments were conducted to study the effect of important design parameters such as flow rate and initial concentration of metal ions, and the maximum sorption capacity was observed at a flow rate of 50 mL h(-1), and Cr(VI) ions concentration 200 mg L(-1) with modified biomass. Experimental data fitted a pseudo-second-order equation. The regeneration performance was observed to be 89.6% and 94.3% for native and modified algal biomass, respectively.

Evaluation of operating conditions for sustainable harvesting of microalgal biomass applying electrochemical method using non sacrificial electrodes.

PubMed

Misra, Rohit; Guldhe, Abhishek; Singh, Poonam; Rawat, Ismail; Stenström, Thor Axel; Bux, Faizal

2015-01-01

The efficient harvesting of microalgae is considered to be one of the challenging steps of algal biofuel production and a key factor limiting the commercial use of microalgae. To overcome the limitation of metallic electrodes depletion, the application of non-sacrificial electrode was investigated for the electrochemical harvesting (ECH) of microalgae. The effect of applied current, addition of electrolyte and initial pH were parameters investigated. The highest recovery efficiency of 83% was obtained for Scenedesmus obliquus at 1.5A, initial pH 9 and 6gL(-)(1) NaCl with power consumption of 3.84kWhkg(-)(1). Recovery efficiency of ECH process was comparable to literature reported centrifugation, filtration and chemical flocculation techniques but with a much lower power consumption. The ECH process with addition of electrolyte enhanced the lipid extraction by 22% without any adverse effects. The ECH process with non sacrificial carbon electrodes could be a possible harvesting step at commercial scale microalgal biomass production. Copyright © 2014 Elsevier Ltd. All rights reserved.

Two-brine model of the genesis of strata-bound Zechstein deposits (Kupferschiefer type), Poland

NASA Astrophysics Data System (ADS)

Kucha, H.; Pawlikowski, M.

1986-01-01

These Kupferschiefer deposits were probably formed as a result of a mixing of two brines. The upper cold brine (UCB) is an unmineralized brine rich in Na, Ca, Cl and SO4, with a pH>7 and originating from evaporites overlying the metal-bearing Zechstein rocks. The lower hot brine (LHB) rich in Mg, K, Cl, SO4 and CO3 with a pH<=7 formed in sediments in the central part of the Zechstein basin at a depth of 7,000 m. This brine was subjected to heating and upward convection toward the Fore-Sudetic monocline along the bottom of the Z1 carbonates. During its migration, it caused albitization, serpentinization and leaching of the primary metal deposits in rocks underlying the Zechstein becoming enriched in heavy metals. The mineralization process, being a result of the mixing of the two brines (UCB and LHB), and catalytic oxidation of the organic matter of the black shale were initiated at shallow depths in the area of the Fore-Sudetic monocline. The boundary of the two brines generally overlapped the strike of the black shale. Parts of the deposit with shale-free host rock suggest that the action of two brines alone was capable of producing economic concentrations of Cu, Pb and Zn. Where the boundary of the two brines overlaps the autooxidation zone (the black shale bottom) and also coincides with γ radiation of thucholite, concentrations of noble metals result. The characteristic vertical distribution of the triplet Cu→Pb→Zn from the bottom upward is universal in the Kupferschiefer environment.

The Role of Bi3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid.

PubMed

Sadeghi, Omid; Amiri, Mehran; Reinheimer, Eric W; Nyman, May

2018-05-22

Metal oxo clusters and metal oxides assemble and precipitate from water in processes that depend on pH, temperature, and concentration. Other parameters that influence the structure, composition, and nuclearity of "molecular" and bulk metal oxides are poorly understood, and have thus not been exploited. Herein, we show that Bi 3+ drives the formation of aqueous Fe 3+ clusters, usurping the role of pH. We isolated and structurally characterized a Bi/Fe cluster, Fe 3 BiO 2 (CCl 3 COO) 8 (THF)(H 2 O) 2 , and demonstrated its conversion into an iron Keggin ion capped by six Bi 3+ irons (Bi 6 Fe 13 ). The reaction pathway was documented by X-ray scattering and mass spectrometry. Opposing the expected trend, increased cluster nuclearity required a pH decrease instead of a pH increase. We attribute this anomalous behavior of Bi/Fe(aq) solutions to Bi 3+ , which drives hydrolysis and condensation. Likewise, Bi 3+ stabilizes metal oxo clusters and metal oxides in strongly acidic conditions, which is important in applications such as water oxidation for energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

WO3 nanoparticle-based conformable pH sensor.

PubMed

Santos, Lídia; Neto, Joana P; Crespo, Ana; Nunes, Daniela; Costa, Nuno; Fonseca, Isabel M; Barquinha, Pedro; Pereira, Luís; Silva, Jorge; Martins, Rodrigo; Fortunato, Elvira

2014-08-13

pH is a vital physiological parameter that can be used for disease diagnosis and treatment as well as in monitoring other biological processes. Metal/metal oxide based pH sensors have several advantages regarding their reliability, miniaturization, and cost-effectiveness, which are critical characteristics for in vivo applications. In this work, WO3 nanoparticles were electrodeposited on flexible substrates over metal electrodes with a sensing area of 1 mm(2). These sensors show a sensitivity of -56.7 ± 1.3 mV/pH, in a wide pH range of 9 to 5. A proof of concept is also demonstrated using a flexible reference electrode in solid electrolyte with a curved surface. A good balance between the performance parameters (sensitivity), the production costs, and simplicity of the sensors was accomplished, as required for wearable biomedical devices.

Chemical and microstructural analyses for heavy metals removal from water media by ceramic membrane filtration.

PubMed

Ali, Asmaa; Ahmed, Abdelkader; Gad, Ali

2017-01-01

This study aims to investigate the ability of low cost ceramic membrane filtration in removing three common heavy metals namely; Pb 2+ , Cu 2+ , and Cd 2+ from water media. The work includes manufacturing ceramic membranes with dimensions of 15 by 15 cm and 2 cm thickness. The membranes were made from low cost materials of local clay mixed with different sawdust percentages of 0.5%, 2.0%, and 5.0%. The used clay was characterized by X-ray diffraction (XRD) and X-ray fluorescence analysis. Aqueous solutions of heavy metals were prepared in the laboratory and filtered through the ceramic membranes. The influence of the main parameters such as pH, initial driving pressure head, and concentration of heavy metals on their removal efficiency by ceramic membranes was investigated. Water samples were collected before and after the filtration process and their heavy metal concentrations were determined by chemical analysis. Moreover, a microstructural analysis using scanning electronic microscope (SEM) was performed on ceramic membranes before and after the filtration process. The chemical analysis results showed high removal efficiency up to 99% for the concerned heavy metals. SEM images approved these results by showing adsorbed metal ions on sides of the internal pores of the ceramic membranes.

Metallaborane reaction chemistry. A predicted and found tailored facile and reversible capture of SO2 by a B-frame-supported bimetallic: structures of [(PMe2Ph)2PtPd(phen)B10H10] and [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10].

PubMed

Bould, Jonathan; Kennedy, John D

2008-06-07

The formally closo twelve-vertex {ortho-M2B10} dimetallaborane system has been predictively tailored for reversible uptake of SO2 across the metal-metal bond, as exemplified by the formation of [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10] from [(PMe2Ph)2PtPd(phen)B10H10].

Biosorption of copper, nickel and manganese using non-living biomass of marine alga, Ulva lactuca.

PubMed

Omar, Hanan Hafez

2008-04-01

The adsorption of Cu2+, Ni2+ and Mn2+ onto the marine algal biomass of Ulva lactuca was investigated in single and multimetal solutions. This study was intended to determine the role of different pH values (2-8) on the biosorption of metals at different concentrations (10, 20 and 30 mg L(-1)). The biosorption capacity of Cu2+, Ni2+ and Mn2+ for 10 mg L(-1) was the same as 20 and 30 mg L(-1), increase with increasing pH up to pH 5.0 and then decreased, in single and multimetal solutions. The optimum pH value was observed in the pH range 4-5 for Cu2+ and pH 5-6 for Ni2+ and Mn2+. The maximum biosorption capacities of tested alga for Cu2+, Ni2+ and Mn2+ were 92, 80 and 75%, respectively in single metal solution at 10 mg L(-1) and pH 5.0. At a further increase of pH (8.0) the biosorption process for Cu2+, Ni2+ and Mn2+ (75, 69 and 63%, respectively at 10 mg L(-1)) was decreased. The minimum biosorptions were 60, 49 and 44% for Cu2+, Ni2+ and Mn2+, respectively in single metal solution at 10 mg L(-1) and pH 2.0. In the multimetal solution, algal biomass exhibited the maximum and the minimum biosorption capacity at different pH values the same as in single metal solution. The inhibitory role of other ions on sorption process can be well observed in multimetal mixture, where biosorption capacity of Cu2+, Ni2+ and Mn2+ were significantly decreased in the multimetal solutions. The maximum biosorption was recorded for Cu2+ (83%) in solution of Cu2+ + Mn2+, Mn2+ (67%) in solution of Ni2 + Mn2+ and for Ni2+ (74%) in solution of Ni2+ + Mn2+ at the concentration 10 mg L(-1) and pH 5.0. The observed reduction in the biosorption of Cu2+, Ni2+ and Mn2+ (65, 57 and 52%, respectively at 10 mg L(-1) and pH 5.0) was more pronounced in the multimetal solution of Cu2 + Ni2+ + Mn2+ as compared with single metal solution. The results demonstrated that the affinity of the tested alga for sorption of the investigated metal ions in single and multimetal solutions runs in the order Cu2+ > Ni2+ > Mn2+. Biosorption equilibrium was established by the Langmuir and Freundlich isotherm models. According to the analyses conducted, the biosorption of Cu2+, Ni2+ and Mn2+ to Ulva lactuca was more consistent with Freundlich isotherm.

Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal-Organic Frameworks.

PubMed

Moon, Su-Young; Wagner, George W; Mondloch, Joseph E; Peterson, Gregory W; DeCoste, Jared B; Hupp, Joseph T; Farha, Omar K

2015-11-16

The nerve agent VX is among the most toxic chemicals known to mankind, and robust solutions are needed to rapidly and selectively deactivate it. Herein, we demonstrate that three Zr6-based metal-organic frameworks (MOFs), namely, UiO-67, UiO-67-NH2, and UiO-67-N(Me)2, are selective and highly active catalysts for the hydrolysis of VX. Utilizing UiO-67, UiO-67-NH2, and UiO-67-N(Me)2 in a pH 10 buffered solution of N-ethylmorpholine, selective hydrolysis of the P-S bond in VX was observed. In addition, UiO-67-N(Me)2 was found to catalyze VX hydrolysis with an initial half-life of 1.8 min. This half-life is nearly 3 orders of magnitude shorter than that of the only other MOF tested to date for hydrolysis of VX and rivals the activity of the best nonenzymatic materials. Hydrolysis utilizing Zr-based MOFs is also selective and facile in the absence of pH 10 buffer (just water) and for the destruction of the toxic byproduct EA-2192.

Cadmium-109 Radioisotope Adsorption onto Polypyrrole Coated Sawdust of Dryobalanops aromatic: Kinetics and Adsorption Isotherms Modelling

PubMed Central

Olatunji, Michael Adekunle; Khandaker, Mayeen Uddin; Amin, Yusoff Mohd; Mahmud, Habibun Nabi Muhammad Ekramul

2016-01-01

A radiotracer study was conducted to investigate the removal characteristics of cadmium (109Cd) from aqueous solution by polypyrrole/ sawdust composite. Several factors such as solution pH, sorbent dosage, initial concentration, contact time, temperature and interfering metal ions were found to have influence on the adsorption process. The kinetics of adsorption was relatively fast, reaching equilibrium within 3 hours. A lowering of the solution pH reduced the removal efficiency from 99.3 to ~ 46.7% and an ambient temperature of 25°C was found to be optimum for maximum adsorption. The presence of sodium and potassium ions inhibited 109Cd removal from its aqueous solution. The experimental data for 109Cd adsorption showed a very good agreement with the Langmuir isotherm and a pseudo-first order kinetic model. The surface condition of the adsorbent before and after cadmium loading was investigated using BET, FESEM and FTIR. Considering the low cost of the precursor’s materials and the toxicity of 109Cd radioactive metal, polypyrrole synthesized on the sawdust of Dryobalanops aromatic could be used as an efficient adsorbent for the removal of 109Cd radioisotope from radionuclide-containing effluents. PMID:27706232

Poly(acrylic acid) modifying bentonite with in-situ polymerization for removing lead ions.

PubMed

He, Y F; Zhang, L; Yan, D Z; Liu, S L; Wang, H; Li, H R; Wang, R M

2012-01-01

In this paper, a new kind of poly(acrylic acid) modified clay adsorbent, the poly(acrylic acid)/bentonite composite (PAA/HB) was prepared by in-situ polymerization, and utilized to remove lead(II) ions from solutions. The maximum adsorption of adsorbent is at pH 5 for metal ions, whereas the adsorption starts at pH 2. The effects of contact time (5-60 min), initial concentration of metal ions (200-1,000 mg/L) and adsorbent dosage (0.04-0.12 g/100 mL) have been reported in this article. The experimental data were investigated by means of kinetic and equilibrium adsorption isotherms. The kinetic data were analyzed by the pseudo-first-order and pseudo-second-order equation. The experimental data fitted the pseudo-second-order kinetic model very well. Langmuir and Freundlich isotherms were tried for the system to better understand the adsorption isotherm process. The maximal adsorption capacity of the lead(II) ions on the PAA/HB, as calculated from the Langmuir model, was 769.2 mg/g. The results in this study indicated that PAA/HB was an attractive candidate for removing lead(II) (99%).

Adsorption of Pb(ll) and Eu(III) by oxide minerals in the presence of natural and synthetic hydroxamate siderophores.

PubMed

Kraemer, Stephan M; Xu, Jide; Raymond, Kenneth N; Sposito, Garrison

2002-03-15

Trihydroxamate siderophores have been proposed for use as mediators of actinide and heavy metal mobility in contaminated subsurface zones. These microbially produced ligands, common in terrestrial and marine environments, recently have been derivatized synthetically to enhance their affinity for transuranic metal cations. However, the interactions between these synthetic derivative and adsorbed trace metals have not been characterized. In this paper we compare a natural siderophore, desferrioxamine-B (DFO-B), with its actinide-specific catecholate derivative, N-(2,3-dihydroxy-4-(methylamido)benzoyl)desferrioxamine-B (DFOMTA), as to their effect on the adsorption of Pb(II) and Eu(III) by goethite and boehmite. In the presence of 240 microM DFO-B, a strongly depleting effect on Eu(III) adsorption by goethite and boehmite occurred above pH 6. By contrast, almost total removal of Eu(III) from solution in the neutral to slightly acidic pH range was observed in the presence of either 10 or 100 microM DFOMTA, due primarilyto the formation of metal-DFOMTA precipitates. Addition of DFOMTA caused an increase in Pb(II) adsorption by goethite below pH 5, but a decrease above pH 5, such that the Pb(II) adsorption edge in the presence of DFOMTA strongly resembled the DFOMTA adsorption envelope, which showed a maximum near pH 5 and decreasing adsorption toward lower and higher pH.

Treatment of industrial wastewater containing Congo Red and Naphthol Green B using low-cost adsorbent.

PubMed

Attallah, M F; Ahmed, I M; Hamed, Mostafa M

2013-02-01

The present work investigates the potential use of metal hydroxides sludge (MHS) generated from hot dipping galvanizing plant for adsorption of Congo Red and Naphthol Green B dyes from aqueous solutions. Characterization of MHS included infrared and X-ray fluorescence analysis. The effect of shaking time, initial dye concentration, temperature, adsorbent dosage and pH has been investigated. The results of adsorption experiments indicate that the maximum capacity of Congo Red and Naphthol Green B dyes at equilibrium (q(e)) and percentage of removal at pH 6 are 40 mg/g, 93 %, and 10 mg/g, 52 %, respectively. Some kinetic models were used to illustrate the adsorption process of Congo Red and Naphthol Green B dyes using MHS waste. Thermodynamic parameters such as (ΔG, ΔS, and ΔH) were also determined.

Removal of chromium from aqueous solutions by diatomite treated with microemulsion.

PubMed

Dantas, T N; Dantas Neto, A A; Moura, M C

2001-06-01

In order to evaluate the sorption of heavy metals, a crude diatomite was impregnated with a microemulsion which showed remarkable increase in chromium sorption capacity as compared to untreated diatomite. Samples with two different granulometries were investigated, both yielding practically complete adsorption. The adsorption process is pH dependent and the best results for the initial Cr (III) concentration of 1.5 g/L were obtained at pH 2.95. The effect of the concentration of the chromium synthetic solution was also investigated. The adsorption isotherms were obtained (30. 40 and 50 degrees C) and the Freundlich and Langmuir models were used to determine the adsorption capacity of the adsorbent. Following the adsorption step, a desorption process was carried out using several eluant solutions. The best results were obtained using hydrochloric acid (100%) as eluant.

Adsorption of aliphatic polyhydroxy carboxylic acids on gibbsite: pH dependency and importance of adsorbate structure.

PubMed

Schneckenburger, Tatjana; Riefstahl, Jens; Fischer, Klaus

2018-01-01

Aliphatic (poly)hydroxy carboxylic acids [(P)HCA] occur in natural, e.g. soils, and in technical (waste disposal sites, nuclear waste repositories) compartments . Their distribution, mobility and chemical reactivity, e.g. complex formation with metal ions and radionuclides, depend, among others, on their adsorption onto mineral surfaces. Aluminium hydroxides, e.g. gibbsite [α-Al(OH) 3 ], are common constituents of related solid materials and mimic the molecular surface properties of clay minerals. Thus, the study was pursued to characterize the adsorption of glycolic, threonic, tartaric, gluconic, and glucaric acids onto gibbsite over a wide pH and (P)HCA concentration range. To consider specific conditions occurring in radioactive wastes, adsorption applying an artificial cement pore water (pH 13.3) as solution phase was investigated additionally. The sorption of gluconic acid at pH 4, 7, 9, and 12 was best described by the "two-site" Langmuir isotherm, combining "high affinity" sorption sites (adsorption affinity constants [Formula: see text] > 1 L mmol -1 , adsorption capacities < 6.5 mmol kg -1 ) with "low affinity" sites ([Formula: see text] < 0.1 L mmol -1 , adsorption capacities ≥ 19 mmol kg -1 ). The total adsorption capacities at pH 9 and 12 were roughly tenfold of that at pH 4 and 7. The S-shaped pH sorption edge of gluconic acid was modelled applying a constant capacitance model, considering electrostatic interactions, hydrogen bonding, surface complex formation, and formation of solved polynuclear complexes between Al 3+ ions and gluconic acid. A Pearson and Spearman rank correlation between (P)HCA molecular properties and adsorption parameters revealed the high importance of the size and the charge of the adsorbates. The adsorption behaviour of (P)HCAs is best described by a combination of adsorption properties of carboxylic acids at acidic pH and of polyols at alkaline pH. Depending on the molecular properties of the adsorbates and on pH, electrostatic interactions, hydrogen bonding, and ternary surface complexation contribute in varying degrees to the adsorption process. Linear distribution coefficients K d between 8.7 and 60.5 L kg -1 (1 mmol L -1 initial PHCA concentration) indicate a considerable mineral surface affinity at very high pH, thus lowering the PHCA fraction available for the complexation of metal ions including radionuclides in solution and their subsequent mobilization.

Leaf responsiveness of Populus tremula and Salix viminalis to soil contaminated with heavy metals and acidic rainwater.

PubMed

Hermle, Sandra; Vollenweider, Pierre; Günthardt-Goerg, Madeleine S; McQuattie, Carolyn J; Matyssek, Rainer

2007-11-01

Fast-growing trees such as Salix viminalis L. and Populus tremula L. are well suited to phytoremediate heavy metal contaminated soils. However, information on tree performance, particularly leaf function, under conditions of heavy metal contamination is scarce. We used yearly coppiced saplings of S. viminalis and P. tremula growing in model ecosytems to test four hypotheses: (1) heavy metal contamination impairs photosynthesis by injuring leaf structure; (2) the effects of heavy metal contamination are enhanced by acidified rainwater and low soil pH; (3) heavy metal contamination increases dark respiration and, thus, repair processes; and (4) heavy metal contamination is tolerated and remediated better by S. viminalis than by P. tremula. We investigated heavy metal accumulation, tissue injury and gas exchange in leaves of plants subjected to controlled soil contamination with heavy metal dust. Additional treatments included acidic and calcareous natural forest subsoils in combination with irrigation with rainwater at pH 5.5 or 3.5. In both provenances of P. tremula that were studied, but not in S. viminalis, heavy metal treatment reduced photosynthesis and transpiration by varying amounts, except in the hot and dry summer of 2003, but had no effect on dark respiration. At light saturation, net CO(2) uptake and water-use efficiency were reduced by heavy metal contamination, whereas the CO(2) concentration in the leaf intercellular air space was increased. Rainwater pH and subsoil pH only slightly modified the effects of the heavy metal treatment on P. tremula. Gas exchange responses of P. tremula to heavy metals were attributed to leaf structural and ultrastructural changes resulting from hypersensitive-response-like processes and accelerated mesophyll cell senescence and necroses in the lower epidermis, especially along the transport pathways of heavy metals in the leaf lamina. Overall, the effects of heavy metals on P. tremula corroborated Hypothesis 1, but refuted Hypotheses 2 and 3, and were inconclusive for Hypothesis 4. Both P. tremula and S. viminalis showed appreciable potential for storing heavy metals in aging foliage.

Transport and deposition of Suwannee River Humic Acid/Natural Organic Matter formed silver nanoparticles on silica matrices: the influence of solution pH and ionic strength.

PubMed

Akaighe, Nelson; Depner, Sean W; Banerjee, Sarbajit; Sohn, Mary

2013-07-01

The transport and deposition of silver nanoparticles (AgNPs) formed from Ag(+) reduction by Suwannee River Humic Acid (SRHA) and Suwannee River Natural Organic Matter (SRNOM) utilizing a silica matrix is reported. The morphology and stability of the AgNPs was analyzed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements. The percentage conversion of the initial [Ag(+)] to [AgNPs] was determined from a combination of atomic absorption (AAS) and UV-Vis spectroscopy, and centrifugation techniques. The results indicate higher AgNP transport and consequently low deposition in the porous media at basic pH conditions and low ionic strength. However, at low acidic pH and high ionic strength, especially with the divalent metallic cations, the mobility of the AgNPs in the porous media was very low, most likely due to NP aggregation. Overall, the results suggest the potential for AgNP contamination of subsurface soils and groundwater aquifers is mostly dependent on their aggregation state, controlled by the soil water and sediment ionic strength and pH. Copyright © 2013 Elsevier Ltd. All rights reserved.

Controls on accumulation and soil solution partitioning of heavy metals across upland sites in United Kingdom (UK).

PubMed

Zia, Afia; van den Berg, Leon; Ahmad, Muhammad Nauman; Riaz, Muhammad; Zia, Dania; Ashmore, Mike

2018-05-31

A significant body of knowledge suggests that soil solution pH and dissolved organic carbon (DOC) strongly influence metal concentrations and speciation in porewater, however, these effects vary between different metals. This study investigated the factors influencing soil and soil solution concentrations of copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) under field conditions in upland soils from UK having a wide range of pH, DOC and organic matter contents. The study primarily focussed on predicting soil and soil solution metal concentrations from the data on total soil metal concentrations (HNO 3 extracts) and soil and soil solution properties (pH, DOC and organic matter content). We tested the multiple regression models proposed by Tipping et al. (2003) to predict heavy metal concentrations in soil solutions and the results indicated a better fit (higher R 2 values) in both studies for Pb compared to the Zn and Cu concentrations. Both studies observed consistent negative relationships of metals with pH and loss on ignition (LOI) suggesting an increase in soil solution metal concentrations with increasing acidity. The positive relationship between Pb concentrations in porewater and HNO 3 extracts was similar for both studies, however, similar relationships were not found for the Zn and Cu concentrations because of the negative coefficients for these metals in our study. The results of this study conclude that the predictive equations of Tipping et al. (2003) may not be applicable to the field sites where the range of DOC and metal concentrations is much lower than their study. Our study also suggests that the extent to which metals are partitioned into soil solution is lower in soils with a higher organic matter contents due to binding of these metals to soil organic matter. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pork Quality Traits According to Postmortem pH and Temperature in Berkshire

PubMed Central

Kim, Tae Wan; Kim, Chul Wook; Yang, Mi Ra; No, Gun Ryoung; Kim, Il-Suk

2016-01-01

This study was performed to investigate the role of pH and temperature postmortem, and to demonstrate the importance of these factors in determining meat quality. Postmortem pH45min (pH at 45 min postmortem or initial pH) via analysis of Pearson’s correlation showed high positive correlation with pH change pHc24 (pH change from pH45min to pH24h postmortem). However, postmortem pH after 24 h (pH24h or ultimate pH) had a high negative correlation with pH change, pHc24, CIE L*, and protein content. Initial temperature postmortem (T1h ) was positively associated with a change in temperature from 45 min to 24 h postmortem (Tc24) and cooking loss, but negatively correlated with water holding capacity. Temperature at 24 h postmortem (T24h) was negatively associated with Tc24. Collectively, these results indicate that higher initial pH was associated with higher pHc24, T1h, and Tc24. However, higher initial pH was associated with a reduction in carcass weight, backfat thickness, CIE a* and b*, water holding capacity, collagen and fat content, drip loss, and cooking loss as well as decreased shear force. In contrast, CIE a* and b*, drip loss, cooking loss, and shear force in higher ultimate pH was showed by a similar pattern to higher initial pH, whereas pHc24, carcass weight, backfat thickness, water holding capacity, fat content, moisture content, protein content, T1h, T24h, and Tc24 were exhibited by completely differential patterns (p<0.05). Therefore, we suggest that initial pH, ultimate pH, and temperatures postmortem are important factors in determining the meat quality of pork. PMID:27499661

Factors affecting adsorption characteristics of Zn2+ on two natural zeolites.

PubMed

Oren, Ali Hakan; Kaya, Abidin

2006-04-17

Mining-related and industrial wastes are primary sources of heavy metal contamination in soils and groundwater. The limitation of such waste in drinking water needs to meet government requirements in order to safeguard human health and environment. Zinc, one of the most preponderant pollutants, is difficult to remove from wastewater rather than other heavy metals (i.e. lead, copper and cadmium). This paper investigates Zn2+ adsorption characteristics of two natural zeolites found in the regions of Gordes and Bigadic, in western Turkey. The results show that the Zn2+ adsorption behavior of both zeolites is highly dependent on the pH. Adsorption dependence on lower pH values (pH<4) is explained by the dissolution of crystal structure and the competition of the zinc ions with the H+. Between pH 4 and 6, the basic mechanism is the ion exchange process. The results also showed that decrease in grain size does not increase the adsorption capacity of zeolite from Gordes, yet it increases that of zeolite from Bigadic about 23%. The results also reveal that an increase in the initial concentration of Zn2+ in the system causes an increase in the adsorption capacity to a degree, then it becomes more constant at higher concentrations. With this, the removal efficiency of Gordes zeolite is two times higher than that of Bigadic zeolite. Results show that an increase in slurry concentration results in a lower uptake of Zn2+. In the final part of the paper, we compared the experimental data with the Langmuir and Freundlich isotherms. The results show that there is a good fit between the experimental data and empirical isotherms.

The Drenchwater deposit, Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn-Pb-Ag deposit

USGS Publications Warehouse

Graham, G.E.; Kelley, K.D.

2009-01-01

The Drenchwater shale-hosted Zn-Pb-Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ??? 4.3, Zn ??? 1400 ??g/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7-3.1) and very metal-rich waters (up to 2600 ??g/L Zn, ??? 260 ??g/L Cu and ???89 ??g/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Biosorption and desorption of Cd2+ from wastewater by dehydrated shreds of Cladophora fascicularis

NASA Astrophysics Data System (ADS)

Deng, Liping; Zhu, Xiaobin; Su, Yingying; Su, Hua; Wang, Xinting

2008-02-01

The adsorption and desorption of algae Cladophora fascicularis and their relation with initial Cd2+ concentration, initial pH, and co-existing ions were studied. Adsorption equilibrium and biosorption kinetics were established from batch experiments. The adsorption equilibrium was adequately described by the Langmuir isotherm, and biosorption kinetics was in pseudo-second order model. The experiment on co-existing ions showed that the biosorption capacity of biomass decreased with an increasing concentration of competing ions. Desorption experiments indicated that EDTA was efficient desorbent for recovery from Cd2+. With high capacities of metal biosorption and desorption, the biomass of Cladophora fascicularis is promising as a cost-effective biosorbent for the removal of Cd2+ from wastewater.

Heavy metals adsorption by novel EDTA-modified chitosan-silica hybrid materials.

PubMed

Repo, Eveliina; Warchoł, Jolanta K; Bhatnagar, Amit; Sillanpää, Mika

2011-06-01

Novel adsorbents were synthesized by functionalizing chitosan-silica hybrid materials with (ethylenediaminetetraacetic acid) EDTA ligands. The synthesized adsorbents were found to combine the advantages of both silica gel (high surface area, porosity, rigid structure) and chitosan (surface functionality). The Adsorption potential of hybrid materials was investigated using Co(II), Ni(II), Cd(II), and Pb(II) as target metals by varying experimental conditions such as pH, contact time, and initial metal concentration. The kinetic results revealed that the pore diffusion process played a key role in adsorption kinetics, which might be attributed to the porous structure of synthesized adsorbents. The obtained maximum adsorption capacities of the hybrid materials for the metal ions ranged from 0.25 to 0.63 mmol/g under the studied experimental conditions. The adsorbent with the highest chitosan content showed the best adsorption efficiency. Bi-Langmuir and Sips isotherm model fitting to experimental data suggested the surface heterogeneity of the prepared adsorbents. In multimetal solutions, the hybrid adsorbents showed the highest affinity toward Pb(II). Copyright © 2011 Elsevier Inc. All rights reserved.

Treatment of As(V) and As(III) by electrocoagulation using Al and Fe electrode.

PubMed

Kuan, W H; Hu, C Y; Chiang, M C

2009-01-01

A batch electrocoagulation (EC) process with bipolar electrode and potentiodynamic polarization tests with monopolar systems were investigated as methods to explore the effects of electrode materials and initial solution pH on the As(V) and As(III) removal. The results displayed that the system with Al electrode has higher reaction rate during the initial period from 0 to 25 minutes than that of Fe electrode for alkaline condition. The pH increased with the EC time because the As(V) and As(III) removal by either co-precipitation or adsorption resulted in that the OH positions in Al-hydroxide or Fe-hydroxide were substituted by As(V) and As(III). The pH in Fe electrode system elevate higher than that in Al electrode because the As(V) removal substitutes more OH position in Fe-hydroxide than that in Al-hydroxide. EC system with Fe electrode can successfully remove the As(III) but system with Al electrode cannot because As(III) can strongly bind to the surface of Fe-hydroxide with forming inner-sphere species but weakly adsorb to the Al-hydroxide surface with forming outer-sphere species. The acidic solution can destroy the deposited hydroxide passive film then allow the metallic ions liberate into the solution, therefore, the acidic initial solution can enhance the As(V) and As(III) removal. The over potential calculation and potentiodynamic polarization tests reveal that the Fe electrode systems possess higher over potential and pitting potential than that of Al electrode system due to the fast hydrolysis of and the occurrence of Fe-hydroxide passive film.

A Class of Multiresponsive Colorimetric and Fluorescent pH Probes via Three Different Reaction Mechanisms of Salen Complexes: A Selective and Accurate pH Measurement.

PubMed

Cheng, Jinghui; Gou, Fei; Zhang, Xiaohong; Shen, Guangyu; Zhou, Xiangge; Xiang, Haifeng

2016-09-19

We report a class of multiresponsive colorimetric and fluorescent pH probes based on three different reaction mechanisms including cation exchange, protonation, and hydrolysis reaction of K(I), Ca(II), Zn(II), Cu(II), Al(III), and Pd(II) Salen complexes. Compared with traditional pure organic pH probes, these complex-based pH probes exhibited a much better selectivity due to the shielding function of the filled-in metal ion in the complex. Their pH sensing performances were affected by the ligand structure and the central metal ion. This work is the first report of "off-on-on'-off" colorimetric and fluorescent pH probes that possess three different reaction mechanisms and should inspire the design of multiple-responsive probes for important analytes in biological systems.

[Use of dinoflagellates as a metal toxicity assessment tool in aquatic system].

PubMed

Yuan, Li-juan; He, Meng-chang

2009-10-15

Although dinoflagellates have been used to assess biological toxicity of contaminants, this method still lacks of corresponding toxicity assessment standard. This study appraised the toxicity of selected heavy metals to dinoflagellates based on the dinoflagellates bioluminescence with QwikLite developed by the United States Navy. The results show that single heavy metal biological toxicity is in the order: Hg2+ > Cu2+ > Cd2+ > As5+ > Pb2+ > Cr6+; Two, three and four heavy metal mixture experiments show synergism primarily, antagonism is in minority. pH has not remarkable effect on dinoflagellates, they can be applied directly in natural water, but pH influence Hg2+ and Cu2+ toxicity greatly, eliminating the influence of pH is essential when doing these two kind of ions measurements. The nutrients has little influence on dinoflagellates, change in COD has obvious effect on the response relationships between dinoflagellates and Hg2+ or CU2+. Metal toxicity assessment using dinoflagellates shows great sensitivity, narrow response scope and high stability. Dinoflagellates are good species for heavy metal biological toxicity test in aquatic system.

High performance of treated and washed MSWI bottom ash granulates as natural aggregate replacement within earth-moist concrete.

PubMed

Keulen, A; van Zomeren, A; Harpe, P; Aarnink, W; Simons, H A E; Brouwers, H J H

2016-03-01

Municipal solid waste incineration bottom ash was treated with specially designed dry and wet treatment processes, obtaining high quality bottom ash granulate fractions (BGF) suitable for up to 100% replacement of natural gravel in concrete. The wet treatment (using only water for separating and washing) significantly lowers the leaching of e.g. chloride and sulfate, heavy metals (antimony, molybdenum and copper) and dissolved organic carbon (DOC). Two potential bottom ash granulate fractions, both in compliance with the standard EN 12620 (aggregates for concrete), were added into earth-moist concrete mixtures. The fresh and hardened concrete physical performances (e.g. workability, strength and freeze-thaw) of high strength concrete mixtures were maintained or improved compared with the reference mixtures, even after replacing up to 100% of the initial natural gravel. Final element leaching of monolithic and crushed granular state BGF containing concretes, showed no differences with the gravel references. Leaching of all mixtures did not exceed the limit values set by the Dutch Soil Quality Degree. In addition, multiple-life-phase emission (pH static test) for the critical elements of input bottom ash, bottom ash granulate (BGF) and crushed BGF containing concrete were assessed. Simulation pH lowering or potential carbonation processes indicated that metal (antimony, barium, chrome and copper) and sulfate element leaching behavior are mainly pH dominated and controlled, although differ in mechanism and related mineral abundance. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal Ions Removal Using Nano Oxide Pyrolox™ Material

NASA Astrophysics Data System (ADS)

Gładysz-Płaska, A.; Skwarek, E.; Budnyak, T. M.; Kołodyńska, D.

2017-02-01

The paper presents the use of Pyrolox™ containing manganese nano oxides used for the removal of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions. Their concentrations were analyzed using the atomic absorption spectrometer SpectrAA 240 FS (Varian) as well as UV-vis method. For this purpose the static kinetic and equilibrium studies were carried out using the batch technique. The effect of solution pH, shaking time, initial metal ion concentrations, sorbent dosage, and temperature was investigated. The equilibrium data were analyzed using the sorption isotherm models proposed by Freundlich, Langmuir-Freundlich, Temkin, and Dubinin-Radushkevich. The kinetic results showed that the pseudo second order kinetic model was found to correlate the experimental data well. The results indicate that adsorption of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions is strongly dependent on pH. The value of pH 4-7 was optimal adsorption. The time to reach the equilibrium was found to be 24 h, and after this time, the sorption percentage reached about 70%. Kinetics of Cu(II), Zn(II), Cd(II), Pb(II), and U(VI) adsorption on the adsorbent can be described by the pseudo second order rate equation. Nitrogen adsorption/desorption, infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) measurements for adsorbent characterization were performed. Characteristic points of the double layer determined for the studied Pyrolox™ sample in 0.001 mol/dm3 NaCl solution are pHPZC = 4 and pHIEP < 2.

High Throughput Discovery of Solar Fuels Photoanodes in the CuO-V 2 O 5 System

DOE PAGES

Zhou, Lan; Yan, Qimin; Shinde, Aniketa; ...

2015-08-26

Solar photoelectrochemical generation of fuel is a promising energy technology yet the lack of an efficient, robust photoanode remains a primary materials challenge in the development and deployment of solar fuels generators. Metal oxides comprise the most promising class of photoanode materials, but no known material meets the demanding requirements of low band gap energy, photoelectrocatalysis of the oxygen evolution reaction, and stability under highly oxidizing conditions. Here, we report the identification of new photoelectroactive materials through a strategic combination of combinatorial materials synthesis, high-throughput photoelectrochemistry, optical spectroscopy, and detailed electronic structure calculations. We identify 4 photoelectrocatalyst phases - α-Cumore » 2V 2O 7, β-Cu 2V 2O 7, γ-Cu 3V 2O 8, and Cu 11V 6O 26 - with band gap energy at or below 2 eV. The photoelectrochemical properties and 30-minute stability of these copper vanadate phases are demonstrated in 3 different aqueous electrolytes (pH 7, pH 9, and pH 13), with select combinations of phase and electrolyte exhibiting unprecedented photoelectrocatalytic stability for metal oxides with sub-2 eV band gap. Through integration of experimental and theoretical techniques, we determine new structure-property relationships and establish CuO-V 2O 5 as the most prominent composition system for OER photoelectrocatalysts, providing crucial information for materials genomes initiatives and paving the way for continued development of solar fuels photoanodes.« less

Electrochemical treatment of anti-cancer drug carboplatin on mixed-metal oxides and boron doped diamond electrodes: Density functional theory modelling and toxicity evaluation.

PubMed

Barışçı, Sibel; Turkay, Ozge; Ulusoy, Ebru; Soydemir, Gülfem; Seker, Mine Gul; Dimoglo, Anatoli

2018-02-15

This study represents the electrooxidation of anti-cancer drug carboplatin (CrbPt) with different mixed metal oxide (MMO) and boron doped diamond (BDD) electrodes. The most effective anode was found as Ti/RuO 2 with the complete degradation of CrbPt in just 5min. The effect of applied current density, pH and electrolyte concentration on CrbPt degradation has been studied. The degradation of CrbPt significantly increased at the initial stages of the process with increasing current density. However, further increase in current density did not affect the degradation rate. While complete degradation of CrbPt was provided at pH 7, the degradation rates were 49% and 75% at pH 9 and 4, respectively. Besides, increasing supporting electrolyte (Na 2 SO 4 ) concentration provided higher degradation rate but further increase in Na 2 SO 4 concentration did not provide higher degradation rate due to excess amount of SO 4 -2 . According to the DFT calculations, the formation of [Pt(NH 3 ) 2 (H 2 O) 2 ] 2+ and [Pt(NH 3 ) 2 (OH) 2 ] takes place with molecular weights of 265 and 263gmol -1 , respectively. Toxicity of treated samples at BDD and Ti/RuO 2 electrodes has been also evaluated in this study. The results showed that Ti/RuO 2 anode provided zero toxicity at the end of the process. Copyright © 2017 Elsevier B.V. All rights reserved.

Ferrate(VI)-Prompted Removal of Metals in Aqueous Media: Mechanistic Delineation of Enhanced Efficiency via Metal Entrenchment in Magnetic Oxides

EPA Science Inventory

The removal efficiency of heavy metal ions (cadmium(II) – Cd(II), cobalt(II) – Co(II), nickel(II) – Ni(II), and copper(II) – Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)), was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective r...

Characterizing the correlation between dephosphorization and solution pH in a calcined water treatment plant sludge.

PubMed

Zhou, Zhenming; Liu, Qidi; Li, Shuwen; Li, Fei; Zou, Jing; Liao, Xiaobin; Yuan, Baoling; Sun, Wenjie

2018-04-26

This study focused on characterizing the correlation between the dephosphorization process of calcined water treatment plant sludge (C-WTPS) and the solution initial pH in batch experiments. The specific aim was to illustrate the effect of different initial pH on the adsorption and desorption of phosphorous in C-WTPS. In addition, the effects of solution initial pH on the release of ammonia nitrogen and total organic carbon (TOC) from C-WTPS and the change of pH after adsorption were also investigated. The results demonstrated that the initial pH significantly influenced the adsorption of phosphorus on C-WTPS. When initial pH was increased from 3 to 10, the phosphorous absorption capacity reduced by 76.5%. Especially, when the initial pH reached to 11, the phosphorus adsorption capacity became a negative value, indicating that C-WTPS released phosphorus into the solution. The addition of C-WTPS to the solution had little impact on the initial pH of the solution. The absorbed phosphorous on C-WTPS was relatively stable in the pH range of 3 to 10. Nevertheless, when the solution pH was higher than 11, it can be easily released into the solution. Furthermore, by comparison with WTPS, C-WTPS released less ammonia nitrogen and TOC into the solution and adsorbed more phosphorus from the solution in the experimental pH range. Therefore, C-WTPS is more suitable to serve as a cost-effective sorbent for phosphorus removal.

DEVELOPMENT OF THE METAL FINISHING FACILITY RISK SCREENING TOOL

EPA Science Inventory

Enhancement of the US Environmental Protection Agency's
Metal Finishing Facility Risk Screening Tool (MFFRST)

William M. Barrett Jr, Ph.D., P.E. , P.E.; Paul Harten, Ph.D.1, Matt Lorber , Charles Peck , and Steve Schwartz, P.E., Q.E.P.3

Recently, the US Environ...

The effects of ocean acidification and a carbon dioxide capture and storage leak on the early life stages of the marine mussel Perna perna (Linneaus, 1758) and metal bioavailability.

PubMed

Szalaj, D; De Orte, M R; Goulding, T A; Medeiros, I D; DelValls, T A; Cesar, A

2017-01-01

The study assesses the effects of carbon dioxide capture and storage (CCS) leaks and ocean acidification (OA) on the metal bioavailability and reproduction of the mytilid Perna perna. In laboratory-scale experiments, CCS leakage scenarios (pH 7.0, 6.5, 6.0) and one OA (pH 7.6) scenario were tested using metal-contaminated sediment elutriates and seawater from Santos Bay. The OA treatment did not have an effect on fertilisation, while significant effects were observed in larval-development bioassays where only 16 to 27 % of larva developed normally. In treatments that simulated CO 2 leaks, when compared with control, fertilisation success gradually decreased and no larva developed to the D-shaped stage. A fall in pH increased the bioavailability of metals to marine mussels. Larva shell size was significantly affected by both elutriates when compared with seawater; moreover, a significant difference occurred at pH 6.5 between elutriates in the fertilisation bioassay.

Effect of process variables on the sulfate reduction process in bioreactors treating metal-containing wastewaters: factorial design and response surface analyses.

PubMed

Villa-Gomez, D K; Pakshirajan, K; Maestro, R; Mushi, S; Lens, P N L

2015-07-01

The individual and combined effect of the pH, chemical oxygen demand (COD) and SO4 (2-) concentration, metal to sulfide (M/S(2-)) ratio and hydraulic retention time (HRT) on the biological sulfate reduction (SR) process was evaluated in an inverse fluidized bed reactor by factorial design analysis (FDA) and response surface analysis (RSA). The regression-based model of the FDA described the experimental results well and revealed that the most significant variable affecting the process was the pH. The combined effect of the pH and HRT was barely observable, while the pH and COD concentration positive effect (up to 7 and 3 gCOD/L, respectively) enhanced the SR process. Contrary, the individual COD concentration effect only enhanced the COD removal efficiency, suggesting changes in the microbial pathway. The RSA showed that the M/S(2-) ratio determined whether the inhibition mechanism to the SR process was due to the presence of free metals or precipitated metal sulfides.

Removal of heavy metals from fly ash leachate using combined bioelectrochemical systems and electrolysis.

PubMed

Tao, Hu-Chun; Lei, Tao; Shi, Gang; Sun, Xiao-Nan; Wei, Xue-Yan; Zhang, Li-Juan; Wu, Wei-Min

2014-01-15

Based on environmental and energetic analysis, a novel combined approach using bioelectrochemical systems (BES) followed by electrolysis reactors (ER) was tested for heavy metals removal from fly ash leachate, which contained high detectable levels of Zn, Pb and Cu according to X-ray diffraction analysis. Acetic acid was used as the fly ash leaching agent and tested under various leaching conditions. A favorable condition for the leaching process was identified to be liquid/solid ratio of 14:1 (w/w) and leaching duration 10h at initial pH 1.0. It was confirmed that the removal of heavy metals from fly ash leachate with the combination of BESs and ER is feasible. The metal removal efficiency was achieved at 98.5%, 95.4% and 98.1% for Cu(II), Zn(II), and Pb(II), respectively. Results of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) indicated that Cu(II) was reduced and recovered mainly as metal Cu on cathodes related to power production, while Zn(II) and Pb(II) were not spontaneously reduced in BESs without applied voltage and basically electrolyzed in the electrolysis reactors. Copyright © 2013 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lasheen, M.R., E-mail: ragaei24@link.net; El-Sherif, Iman Y., E-mail: iman57us@yahoo.com; Tawfik, Magda E., E-mail: magdaemileta@yahoo.com

Highlights: • Nano magnetite–chitosan films were prepared by casting method. • The efficiency of the prepared films for removing heavy metals was investigated. • The adsorption mechanism was studied using different isotherm and kinetic models. • Films reuse and metals recovery were studied. - Abstract: Nano magnetite chitosan (NMag–CS) film was prepared and characterized with different analytical methods. X-ray diffraction (XRD) patterns confirmed the formation of a pure magnetite structure and NMag–CS nanocomposite. TEM image of the film, revealed the uniform dispersion of magnetite nanoparticles inside chitosan matrix. The adsorption properties of the prepared film for copper, lead, cadmium, chromiummore » and nickel metal ions were evaluated. Different factors affecting the uptake behavior by the composite films such as time, initial pH and film dose were investigated. The adsorption equilibrium attained using 2 g/L of the film after 120 min of reaction. The equilibrium data were analyzed using Langmuir and Freundlich models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all metals. The metals regenerated from films with an efficiency greater than 95% using 0.1 M ethylene diamine tetra acetic acid (EDTA) and films were successfully reused for adsorption.« less

Applications of optically detected MRI for enhanced contrast and penetration in metal

NASA Astrophysics Data System (ADS)

Ruangchaithaweesuk, Songtham; Yu, Dindi S.; Garcia, Nissa C.; Yao, Li; Xu, Shoujun

2012-10-01

We report quantitative measurements using optically detected magnetic resonance imaging (MRI) for enhanced pH contrast and flow inside porous metals. Using a gadolinium chelate as the pH contrast agent, we show the response is 0.6 s-1 mM-1 per pH unit at the ambient magnetic field for the pH range 6-8.5. A stopped flow scheme was used to directly measure T1 relaxation time to determine the relaxivity. Flow profiles and images were obtained for a series of porous metals with different average pore sizes. The signal amplitudes and spatial distributions were compared. A clogged region in one of the samples was revealed using optically detected MRI but not optical imaging or scanning electron microscopy. These applications will significantly broaden the impact of optically detected MRI in chemical imaging and materials research.

Tetracycline adsorption on kaolinite: pH, metal cations and humic acid effects.

PubMed

Zhao, Yanping; Geng, Jinju; Wang, Xiaorong; Gu, Xueyuan; Gao, Shixiang

2011-07-01

Contamination of environmental matrixes by human and animal wastes containing antibiotics is a growing health concern. Because tetracycline is one of the most widely-used antibiotics in the world, it is important to understand the factors that influence its mobility in soils. This study investigated the effects of pH, background electrolyte cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), heavy metal Cu(2+) and humic acid (HA) on tetracycline adsorption onto kaolinite. Results showed that tetracycline was greatly adsorbed by kaolinite over pH 3-6, then decreased with the increase of pH, indicating that tetracycline adsorption mainly through ion exchange of cations species and complexation of zwitterions species. In the presence of five types of cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), tetracycline adsorption decreased in accordance with the increasing of atomic radius and valence of metal cations, which suggested that outer-sphere complexes formed between tetracycline and kaolinite, and the existence of competitor ions lead to the decreasing adsorption. The presence of Cu(2+) greatly enhanced the adsorption probably by acting as a bridge ion between tetracycline species and the edge sites of kaolinite. HA also showed a major effect on the adsorption: at pH < 6, the presence of HA increased the adsorption, while the addition of HA showed little effect on tetracycline adsorption at higher pH. The soil environmental conditions, like pH, metal cations and soil organic matter, strongly influence the adsorption behavior of tetracycline onto kaolinite and need to be considered when assessing the environmental toxicity of tetracycline.

Comparative characterization of sewage sludge compost and soil: Heavy metal leaching characteristics.

PubMed

Fang, Wen; Wei, Yonghong; Liu, Jianguo

2016-06-05

The leaching and accumulation of heavy metals are major concerns following the land application of sewage sludge compost (SSC). We comparatively characterized SSC, the reference soil, and the SSC amended soil to investigate their similarities and differences regarding heavy metal leaching behavior and then to evaluate the effect of SSC land application on the leaching behavior of soil. Results showed that organic matter, including both of particulate organic matter (POM) and dissolved organic matter (DOM), were critical factors influencing heavy metal leaching from both of SSC and the soil. When SSC was applied to soil at the application rate of 48t/ha, the increase of DOM content slightly enhanced heavy metal leaching from the amended soil over the applicable pH domain (6

Treatment of combined acid mine drainage (AMD)--flotation circuit effluents from copper mine via Fenton's process.

PubMed

Mahiroglu, Ayse; Tarlan-Yel, Esra; Sevimli, Mehmet Faik

2009-07-30

The treatability of a copper mine wastewater, including heavy metals, AMD, as well as flotation chemicals, with Fenton process was investigated. Fenton process seems advantageous for this treatment, because of Fe(2+) content and low pH of AMD. First, optimum Fe(2+) condition under constant H(2)O(2) was determined, and initial Fe(2+) content of AMD was found sufficient (120 mg/L for removal of chemical oxygen demand (COD) of 6125 mg/L). In the second step, without any additional Fe(2+), optimum H(2)O(2) dosage was determined as 40 mg/L. Fe(2+)/H(2)O(2) molar ratio of 1.8 was enough to achieve the best treatment performance. In all trials, initial pH of AMD was 4.8 and pH adjustment was not performed. Utilization of existing pH and Fe(2+), low H(2)O(2) requirements, and up to 98% treatment performances in COD, turbidity, color, Cu(2+), Zn(2+) made the proposed treatment system promising. Since the reaction occurs stepwise, a two-step kinetic model was applied and calculated theoretical maximum removal rate was consistent to experimental one, which validates the applied model. For the optimum molar ratio (1.8), 140 mL/L sludge of high density (1.094 g/mL), high settling velocity (0.16 cm/s) with low specific resistance (3.15 x 10(8)m/kg) was obtained. High reaction rates and easily dewaterable sludge characteristics also made the proposed method advantageous.

Sorption interactions of heavy metals with biochar in soil remediation studies

NASA Astrophysics Data System (ADS)

Fristak, Vladimir; Friesl-Hanl, Wolfgang; Wawra, Anna; Soja, Gerhard

2015-04-01

The search for new materials in soil remediation applications has led to new conversion technologies such as carbonization and pyrolysis. Biochar represents the pyrolytic product of different biomass input materials processed at 350-1000°C and anoxic conditions. The pyrolysis temperature and feedstock have a considerable influence on the quality of the charred product and also its main physico-chemical properties. Biochar as porous material with large specific surface and C-stability is utilized in various environmental and agricultural technologies. Carbon sequestration, increase of soil water-holding capacity and pH as well as sorption of different xenobiotics present only a fraction of the multitude of biochar application possibilities. Heavy metals as potential sources of ecotoxicological risks are characterized by their non-degradability and the potential transfer into the food chain. Carbonaceous materials have been used for a long time as sorbents for heavy metals and organic contaminants in soil and water technologies. The similarity of biochar with activated carbon predetermines this material as remediation tool which plays an important role in heavy metal immobilization and retention with a parallel reduction in the risk of ground water and food crop contamination. In all this processes the element-specific sorption behaviour of biochar creates new conditions for pollutant binding. Sorption interaction and separation of contaminants from soil solution or waste effluent can be affected by wide-ranging parameters. In detail, our study was based on batch-sorption comparisons of two biochars produced from wood chips and green waste residues. We observed that sorption efficiency of biochar for model bivalent heavy metals (Cd, Zn, Cu) can be influenced by equilibrium parameters such as pH, contact time, initial concentration of metal in reaction solutions, presence of surfactants and chemical modification by acid hydrolysis, esterification and methylation. The study of sorption mechanisms showed differences in the sorption of the targeted heavy metals in relation to the contribution of ion-exchange and precipitation processes. We confirmed the effectivity of physico-chemical artificial aging on sorption capacity of biochar in terms of changes in surface structure. Based on these results, the application potential of biochar as sorption material for stabilizing heavy metals in soils is discussed.

Geomycology. [fungal biosolubilization and accumulation of metals

NASA Technical Reports Server (NTRS)

Puerner, N. J.; Siegel, S. M.

1976-01-01

Fungi have long been known to have capabilities for reduction and alkylation of arsenate and selenate but their general capabilities for solubilizing and accumulating metallic substances have been given serious attention only in recent years. Common members of the Aspergillaceae cultured on boron, copper, lead and other metals or oxides can solubilize and concentrate the elements or their compounds. To account for biosolubilization of the metals, we have set up a model study, incubating selected metals, e.g., mercury, in solutions of various metabolites including L-lysine and citric acid. Results of 100-300 days incubation showed that many metals can in fact be readily solubilized, and in some cases more effectively at pH 6-7 than at pH 1.5-2.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, W.Y.

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Purification of alkali metal nitrates

DOEpatents

Fiorucci, Louis C.; Gregory, Kevin M.

1985-05-14

A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

Silicene catalyzed reduction of nitrobenzene to aniline: A mechanistic study

NASA Astrophysics Data System (ADS)

Morrissey, Christopher; He, Haiying

2018-03-01

The reduction of nitrobenzene to aniline has broad applications in chemical and pharmaceutical industries. The high reaction temperatures and pressures and unavoidable hazardous chemicals of current metal catalysts call for more environmentally friendly non-metal catalysts. In this study, the plausibility of silicene as a potential catalyst for nitrobenzene reduction is investigated with a focus on the distinct reaction mechanism based on the density functional theory. The direct reaction pathway was shown to be distinctly different from the Haber mechanism following PhNO2∗ → PhNO∗ → PhNHO∗ → PhNH2O∗ → PhNH2∗. The hydroxyl groups remain bound to silicene after aniline is formed and acquire a high activation barrier to remove.

Biosorption of lead, cadmium, and zinc by Citrobacter strain MCM B-181: Characterization studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Puranik, P.R.; Paknikar, K.M.

1999-03-01

The biosorption process for removal of lead, cadmium, and zinc by Citrobacter strain MCM B-181, a laboratory isolate, was characterized. Effects of environmental factors and growth conditions on metal uptake capacity were studied. Pretreatment of biomass with chemical agents increased cadmium sorption efficiency; however, there was no significant enhancement in lead and zinc sorption capacity. Metal sorption by Citrobacter strain MCM B-181 was found to be influenced by the pH of the solution, initial metal concentration, biomass concentration, and type of growth medium. The metal sorption process was not affected by the age of the culture or change in temperature.more » Equilibrium metal sorption was found to fit the Langmuir adsorption model. Kinetic studies showed that metal uptake by Citrobacter strain MCm B-181 was a fast process, requiring < 20 min to achieve > 90% adsorption efficiency. The presence of cations reduced lead, zinc, and cadmium sorption to the extent of 11.8%, 84.3%, and 33.4%, respectively. When biomass was exposed to multimetal solutions, metals were adsorbed in the order Co{sup 2+} < Ni{sup 2+} < Cd{sup 2+} < Cu{sup 2+}, Zn{sup 2+} < Pb{sup 2+}. A new mathematical model used for batch kinetic studies was found to be highly useful in prediction of experimentally obtained metal concentration profiles as a function of time.« less

A simple scheme to determine potential aquatic metal toxicity from mining wastes

USGS Publications Warehouse

Wildeman, T.R.; Smith, K.S.; Ranville, J.F.

2007-01-01

A decision tree (mining waste decision tree) that uses simple physical and chemical tests has been developed to determine whether effluent from mine waste material poses a potential toxicity threat to the aquatic environment. For the chemical portion of the tree, leaching tests developed by the United States Geological Survey, the Colorado Division of Minerals and Geology (Denver, CO), and a modified 1311 toxicity characteristic leaching procedure (TCLP) test of the United States Environmental Protection Agency have been extensively used as a surrogate for readily available metals that can be released into the environment from mining wastes. To assist in the assessment, element concentration pattern graphs (ECPG) are produced that compare concentrations of selected groups of elements from the three leachates and any water associated with the mining waste. The MWDT makes a distinction between leachates or waters with pH less than or greater than 5. Generally, when the pH values are below 5, the ECPG of the solutions are quite similar, and potential aquatic toxicity from cationic metals, such as Pb, Cu, Zn, Cd, and Al, is assumed. Below pH 5, these metals are mostly dissolved, generally are not complexed with organic or inorganic ligands, and hence are more bioavailable. Furthermore, there is virtually no carbonate alkalinity at pH less than 5. All of these factors promote metal toxicity to aquatic organisms. On the other hand, when the pH value of the water or the leachates is above 5, the ECPG from the solutions are variable, and inferred aquatic toxicity depends on factors in addition to the metals released from the leaching tests. Hence, leachates and waters with pH above 5 warrant further examination of their chemical composition. Physical ranking criteria provide additional information, particularly in areas where waste piles exhibit similar chemical rankings. Rankings from physical and chemical criteria generally are not correlated. Examples of how this decision tree has been applied in assessing mine sites are discussed. Copyright ?? Taylor & Francis Group, LLC.

Hydrogeochemical Investigation of the Standard Mine Vicinity, Upper Elk Creek Basin, Colorado

USGS Publications Warehouse

Manning, Andrew H.; Verplanck, Philip L.; Mast, M. Alisa; Wanty, Richard B.

2008-01-01

Ground- and surface-water samples were collected in the vicinity of the Standard Mine in west-central Colorado in order to characterize the local ground-water flow system, determine metal concentrations in local ground water, and better understand factors controlling the discharge of metal-rich waters from the mine. The sampling program included a one-time sampling of springs, mine adits, and exploration pits in Elk Basin and Redwell Basin; repeated sampling throughout one year of Standard Mine Level 1 discharge and Elk Creek near its confluence with Coal Creek; and a one-time sampling of underground sites in Levels 3 and 5 of the Standard Mine. Samples were analyzed for major ions and trace elements, stable isotopes of hydrogen (2H/1H) and oxygen (18O/16O), strontium isotopes, and tritium and dissolved noble gases (including helium isotopes) for tritium/helium-3 age dating. No clear correlations were observed between natural ground-water discharge locations and map-scale faults and lithology. Surface observations and the location of ground-water discharge suggest that simple topography, rather than large-scale geologic features, primarily controls the occurrence and flow of shallow ground water in Elk Basin. Discrete inflows from cross faults or other features were not observed in Levels 3 and 5 of the Standard Mine. Instead, water entered the mine as relatively persistent dripping from gouge and breccia within the Standard fault, which both tunnels follow. Therefore, the Standard fault itself is probably the main pathway of ground-water flow from the shallow subsurface to the mine workings. Low pH (as low as 3.2) and elevated concentrations of zinc, lead, cadmium, copper, and manganese (commonly exceeding water-quality standards for Elk Creek) were measured in samples located within or immediately downgradient of areas where sulfides are abundant, including the Standard fault, the Elk Lode portal, and the breccia pipe in Redwell Basin. Concentrations of these metals were typically low and pH values were circumneutral at surrounding locations. Metal concentrations in samples collected from underground workings in the Standard Mine were also generally higher than in samples collected at aboveground sites located outside of sulfide-rich areas. Metal concentrations in discharge from the Level 1 tunnel were among the highest measured in Elk Basin. All of these observations suggest that sulfide-rich mineralized rock is the primary control on dissolved metal concentrations and pH in ground water in the Standard Mine vicinity. Waste-rock piles apparently exert another major control on metal concentrations and pH; the lowest pH and highest metal concentrations typically are found in discharge from waste-rock piles. Concentrations of several chemical constituents along with strontium isotope data indicate that none of the sampled waters could have been the primary source of metals in discharge from Level 1. Therefore, this study did not identify the primary source location for metals in Level 1 discharge. Possible sources must be located below Levels 3 and 5 or farther back into the mountainside than the ends of Levels 3 and 5. Apparent tritium/helium-3 ground-water ages ranged from 0 to 9 yr, and a considerable majority were <1 yr. Tritium data and computed initial tritium values (measured tritium plus measured tritiogenic helium-3) suggest that much of the ground water in the Standard Mine vicinity was weeks to months old rather than years old. Tritium, d2H, and d18O data from water entering into and discharging from the Standard Mine displayed spatial and temporal patterns indicating that these tracers were influenced by seasonal variations in their concentration in precipitation. The tracer data therefore suggest that ground water entering into and discharging from the Standard Mine was largely composed of water <1 yr old. Pronounced seasonal variations in geochemistry in Level 1 discharge also are consistent with short r

Sorption of Cu and Pb to kaolinite-fulvic acid colloids: Assessment of sorbent interactions

NASA Astrophysics Data System (ADS)

Heidmann, Ilona; Christl, Iso; Kretzschmar, Ruben

2005-04-01

The sorption of Cu(II) and Pb(II) to kaolinite-fulvic acid colloids was investigated by potentiometric titrations. To assess the possible interactions between kaolinite and fulvic acid during metal sorption, experimental sorption isotherms were compared with predictions based on a linear additivity model (LAM). Suspensions of 5 g L -1 kaolinite and 0.03 g L -1 fulvic acid in 0.01 M NaNO 3 were titrated with Cu and Pb solutions, respectively. The suspension pH was kept constant at pH 4, 6, or 8. The free ion activities of Cu 2+ and Pb 2+ were monitored in the titration vessel using ion selective electrodes. Total dissolved concentrations of metals (by ICP-MS) and fulvic acid (by UV-absorption) were determined in samples taken after each titration step. The amounts of metals sorbed to the solid phase, comprised of kaolinite plus surface-bound fulvic acid, were calculated by difference. Compared to pure kaolinite, addition of fulvic acid to the clay strongly increased metal sorption to the solid phase. This effect was more pronounced at pH 4 and 6 than at pH 8, because more fulvic acid was sorbed to the kaolinite surface under acidic conditions. Addition of Pb enhanced the sorption of fulvic acid onto kaolinite at pH 6 and 8, but not at pH 4. Addition of Cu had no effect on the sorption of fulvic acid onto kaolinite. In the LAM, metal sorption to the kaolinite surface was predicted by a two-site, 1-pK basic Stern model and metal sorption to the fulvic acid was calculated with the NICA-Donnan model, respectively. The LAM provided good predictions of Cu sorption to the kaolinite-fulvic acid colloids over the entire range in pH and free Cu 2+ ion activity (10 -12 to 10 -5). The sorption of Pb was slightly underestimated by the LAM under most conditions. A fractionation of the fulvic acid during sorption to kaolinite was observed, but this could not explain the observed deviations of the LAM predictions from the experimental Pb sorption isotherms.

Manufacture and application of RuO2 solid-state metal-oxide pH sensor to common beverages.

PubMed

Lonsdale, W; Wajrak, M; Alameh, K

2018-04-01

A new reproducible solid-state metal-oxide pH sensor for beverage quality monitoring is developed and characterised. The working electrode of the developed pH sensor is based on the use of laser-etched sputter-deposited RuO 2 on Al 2 O 3 substrate, modified with thin layers of sputter-deposited Ta 2 O 5 and drop-cast Nafion for minimisation of redox interference. The reference electrode is manufactured by further modifying a working electrode with a porous polyvinyl butyral layer loaded with fumed SiO 2 . The developed pH sensor shows excellent performance when applied to a selection of beverage samples, with a measured accuracy within 0.08 pH of a commercial glass pH sensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Toxic metals biosorption by Jatropha curcas deoiled cake: equilibrium and kinetic studies.

PubMed

Rawat, Anand P; Rawat, Monica; Rai, J P N

2013-08-01

The equilibrium sorption of Cr(VI) and Cu(II) from aqueous solution using Jatropha curcas deoiled cake, has been studied with respect to adsorbent dosage, contact time, pH, and initial metal concentration in batch mode experiments. Removal of Cu(II) by deoiled cake was greater than that of Cr(VI). The adsorbent chemical characteristics, studied by Fourier transform-infrared analysis, suggested that the presence of Cr(VI) and Cu(II) in the biomass influenced the bands corresponding to hydroxyl and carboxyl groups. Desorption studies revealed that maximum metals recovery was achieved by HNO3 followed by CH3COOH and HCl. The Freundlich isotherm model showed good fit to the equilibrium adsorption data. The adsorption kinetics followed the pseudo-second-order model, which provided the best correlation for the biosorption process, and suggested that J. curcas deoiled cake can be used as an efficient biosorbent over other commonly used sorbents for decontamination of Cr(VI)- and Cu(II)-containing wastewater.

Reversible capture of small molecules on bimetallaborane clusters: synthesis, structural characterization, and photophysical aspects.

PubMed

Bould, Jonathan; Baše, Tomáš; Londesborough, Michael G S; Oro, Luis A; Macías, Ramón; Kennedy, John D; Kubát, Pavel; Fuciman, Marcel; Polívka, Tomáš; Lang, Kamil

2011-08-15

Metallaborane compounds containing two adjacent metal atoms, [(PMe(2)Ph)(4)MM'B(10)H(10)] (where MM' = Pt(2), 1; PtPd, 7; Pd(2), 8), have been synthesized, and their propensity to sequester O(2), CO, and SO(2) and to then release them under pulsed and continuous irradiation are described. Only [(PMe(2)Ph)(4)Pt(2)B(10)H(10)], 1, undergoes reversible binding of O(2) to form [(PMe(2)Ph)(4)(O(2))Pt(2)B(10)H(10)] 3, but solutions of 1, 7, and 8 all quantitatively take up CO across their metal-metal vectors to form [(PMe(2)Ph)(4)(CO)Pt(2)B(10)H(10)] 4, [(PMe(2)Ph)(4)(CO)PtPdB(10)H(10)] 10, and [(PMe(2)Ph)(4)(CO)Pd(2)B(10)H(10)] 11, respectively. Crystallographically determined interatomic M-M distances and infrared CO stretching frequencies show that the CO molecule is bound progressively more weakly in the sequence {PtPt} > {PtPd} > {PdPd}. Similarly, SO(2) forms [(PMe(2)Ph)(4)(SO(2))Pt(2)B(10)H(10)] 5, [(PMe(2)Ph)(4)(SO(2))PtPdB(10)H(10)] 12, and [(PMe(2)Ph)(4)(SO(2))Pd(2)B(10)H(10)] 13 with progressively weaker binding of the SO(2) molecule. The uptake and release of gas molecules are accompanied by changes in their absorption spectra. Nanosecond transient absorption spectroscopy clearly shows that the O(2) and CO molecules are liberated from the bimetallic binding site with high quantum yields of about 0.6. For 3, in addition to dioxygen release in the triplet ground state, singlet oxygen O(2)((1)Δ(g)) was also detected with a quantum yield <0.01. In most cases, the release and rebinding of the gas molecules can be cycled with little photodegradation of the compounds. Femtosecond transient absorption spectroscopy further reveals that the photorelease of the O(2) and CO molecules, from 3 and 4 respectively, is an ultrafast process taking place on a time scale of tens of picoseconds. For SO(2), the release is even faster (<1 ps), but only in the case of mixed metal PtPd adducts, most probably because of the metal-metal bonding asymmetry in the mixed metal clusters; for the corresponding symmetric Pt(2) and Pd(2) adducts, 5 and 13, the release of SO(2) is significantly slower (>1 ns). All these compounds may have potential to serve as light-triggered local and instantaneous sources of the studied gases. © 2011 American Chemical Society

An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

PubMed

Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

2015-04-08

An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.

Microbiologically influenced corrosion of orthodontic metallic appliances.

PubMed

Kameda, Takashi; Oda, Hirotake; Ohkuma, Kazuo; Sano, Natsuki; Batbayar, Nomintsetseg; Terashima, Yukari; Sato, Soh; Terada, Kazuto

2014-01-01

Biocorrosion (microbiologically influenced corrosion; MIC) occur in aquatic habitats varying in nutrient content, temperature, stress and pH. The oral environment of organisms, including humans, should be one of the most hospitable for MIC. Corrosion of metallic appliances in the oral region is one cause of metal allergy in patients. In this study, an inductively coupled plasma-optical emission spectrometer revealed elution of Fe, Cr and Ni from stainless steel (SUS) appliances incubated with oral bacteria. Three-dimensional laser confocal microscopy also revealed that oral bacterial culture promoted increased surface roughness and corrosion pits in SUS appliances. The pH of the supernatant was lowered after co-culture of appliances and oral bacteria in any combinations, but not reached at the level of depassivation pH of their metallic materials. This study showed that Streptococcus mutans and Streptococcus sanguinis which easily created biofilm on the surfaces of teeth and appliances, did corrode orthodontic SUS appliances.

[Determination of total mass and morphology analysis of heavy metal in soil with potassium biphthalate-sodium hydroxide by ICP-AES].

PubMed

Qu, Jiao; Yuan, Xing; Cong, Qiao; Wang, Shuang

2008-11-01

Blank soil was used as quality controlling samples, soil sample dealt by potassium biphthalate-sodium hydroxide buffer solution was used as check sample, mixed acid HNO3-HF-HClO4 was chosen to nitrify soil samples, and plasma emission spectrometer (ICP-AES) was used as detecting method. The authors determined the total metal mass of Mo, Pb, As, Hg, Cr, Cd, Zn, Cu and Ni in the extracted and dealt soil samples, and determined the mass of Mo, Pb, As, Hg, Cr, Cd, Zn, Cu and Ni in the three chemical morphologies, including acid extractable morphology, oxide associated morphology, and organics associated modality. The experimental results indicated that the different pH of potassium biphthalate-sodium hydroxide buffer solution had obvious influence on the total mass of heavy metal and morphology transformation. Except for metal element Pb and Zn, the addition of different pH potassium dihydrogen phosphate-sodium hydroxide buffer solution could accelerate the soil samples nitrification and the total mass determination of heavy metal in the soil samples. The potassium biphthalate-sodium hydroxide buffer solution could facilitate the acid extractable morphology of Cr, Cu, Hg and Pb, oxidation associated morphology of As, Hg, Pb and Zn and the organic associated morphology transforming of As and Hg. At pH 5.8, the maximum acid extractable morphology contents of Cu and Hg were 2.180 and 0.632 mg x kg(-1), respectively; at pH 6.2, the maximal oxidation associated morphology content of Pb could achieve 27.792 mg x kg(-1); at pH 6.0, the maximum organic associated morphology content of heavy metal Hg was 4.715 mg x kg(-1).

Ocean acidification modulates the incorporation of radio-labeled heavy metals in the larvae of the Mediterranean sea urchin Paracentrotus lividus.

PubMed

Dorey, Narimane; Martin, Sophie; Oberhänsli, François; Teyssié, Jean-Louis; Jeffree, Ross; Lacoue-Labarthe, Thomas

2018-10-01

The marine organisms which inhabit the coastline are exposed to a number of anthropogenic pressures that may interact. For instance, the accumulation of toxic metals present in coastal waters is expected to be modified by ocean acidification through e.g. changes in physiological performance and/or elements availability. Changes in bioaccumulation due to lowering pH are likely to be differently affected depending on the nature (essential vs. non-essential) and speciation of each element. The Mediterranean is of high concern for possible cumulative effects due to strong human influences on the coastline. The aim of this study was to determine the effect of ocean acidification (from pH 8.1 down to -1.0 pH units) on the incorporation kinetics of six trace metals (Mn, Co, Zn, Se, Ag, Cd, Cs) and one radionuclide ( 241 Am) in the larvae of an economically- and ecologically-relevant sea urchin of the Mediterranean coastline: Paracentrotus lividus. The radiolabelled metals and radionuclides added in trace concentrations allowed precise tracing of their incorporation in larvae during the first 74 h of their development. Independently of the expected indirect effect of pH on larval size/developmental rates, Paracentrotus lividus larvae exposed to decreasing pHs incorporated significantly more Mn and Ag and slightly less Cd. The incorporation of Co, Cs and 241 Am was unchanged, and Zn and Se exhibited complex incorporation behaviors. Studies such as this are necessary prerequisites to the implementation of metal toxicity mitigation policies for the future ocean. We discuss possible reasons and mechanisms for the specific effect of pH on each metals. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multi-decadal Records of Ocean Acidification and Toxic Heavy Metal Pollution in Coral Cores from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Stewart, J.; Tolliver, R.; Field, D. B.; Young, C.; Stafford, G.; Day, R. D.

2016-12-01

Monitoring of the physiological/ecological response of marine calcifying organisms to the combination of lower pH and toxic metal pollutants (e.g. Cu and Sn from boat anti-fouling paints) into the oceans requires detailed knowledge of the rates and spatial distribution of ocean acidification (OA) and trace metal composition over time. Yet, measurement of metal concentrations and carbonate system parameters in the modern ocean from seawater bottle data is patchy (e.g. CDIAC/WOCE Carbon Data; http://cdiac.ornl.gov) and there remain few long-term surface water pH monitoring stations; the two longest continuous records of ocean pH extend back less than 30 years (Bermuda - BATS, 31°40'N, 64°10'W; Hawaii - HOTs, 22°45'N, 158°00'W). Much attention has therefore been focused on trace metal and ocean carbonate system proxy development to allow reconstruction of seawater metal content and pH in the past. Of particular promise is the boron isotope (δ11B) pH-proxy measured in marine calcifying organisms such as coral that can be cored enabling multi-decadal, annual-resolution, records of trace element incorporation and seawater pH to be generated. Here we present continuous Cu/Ca and Sn/Ca records in addition to δ11B data from three coral cores of Porites lutea. collected from waters proximal to Oahu, Hawaii. The diagenetic integrity of samples is verified using X-ray diffraction to assess the degree of calcite replacement. These cores reach a maximum depth of 80 cm and represent approximately 80 years of coral growth and seawater chemistry.

Heavy Metal Adsorption onto Kappaphycus sp. from Aqueous Solutions: The Use of Error Functions for Validation of Isotherm and Kinetics Models

PubMed Central

Rahman, Md. Sayedur; Sathasivam, Kathiresan V.

2015-01-01

Biosorption process is a promising technology for the removal of heavy metals from industrial wastes and effluents using low-cost and effective biosorbents. In the present study, adsorption of Pb2+, Cu2+, Fe2+, and Zn2+ onto dried biomass of red seaweed Kappaphycus sp. was investigated as a function of pH, contact time, initial metal ion concentration, and temperature. The experimental data were evaluated by four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) and four kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models). The adsorption process was feasible, spontaneous, and endothermic in nature. Functional groups in the biomass involved in metal adsorption process were revealed as carboxylic and sulfonic acids and sulfonate by Fourier transform infrared analysis. A total of nine error functions were applied to validate the models. We strongly suggest the analysis of error functions for validating adsorption isotherm and kinetic models using linear methods. The present work shows that the red seaweed Kappaphycus sp. can be used as a potentially low-cost biosorbent for the removal of heavy metal ions from aqueous solutions. Further study is warranted to evaluate its feasibility for the removal of heavy metals from the real environment. PMID:26295032

Kinetic and thermodynamic studies on the adsorption of heavy metals from aqueous solution by melanin nanopigment obtained from marine source: Pseudomonas stutzeri.

PubMed

Manirethan, Vishnu; Raval, Keyur; Rajan, Reju; Thaira, Harsha; Balakrishnan, Raj Mohan

2018-05-15

The difficulty in removal of heavy metals at concentrations below 10 mg/L has led to the exploration of efficient adsorbents for removal of heavy metals. The adsorption capacity of biosynthesized melanin for Mercury (Hg(II)), Chromium (Cr(VI)), Lead (Pb(II)) and Copper (Cu(II)) was investigated at different operating conditions like pH, time, initial concentration and temperature. The heavy metals adsorption process was well illustrated by the Lagergren's pseudo-second-order kinetic model and the equilibrium data fitted excellently to Langmuir isotherm. Maximum adsorption capacity obtained from Langmuir isotherm for Hg(II) was 82.4 mg/g, Cr(VI) was 126.9 mg/g, Pb(II) was 147.5 mg/g and Cu(II) was 167.8 mg/g. The thermodynamic parameters revealed that the adsorption of heavy metals on melanin is favorable, spontaneous and endothermic in nature. Binding of heavy metals on melanin surface was proved by Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Contemplating the results, biosynthesized melanin can be a potential adsorbent for efficient removal of Hg(II), Cr(VI), Pb(II) and Cu(II) ions from aqueous solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Heavy Metal Adsorption onto Kappaphycus sp. from Aqueous Solutions: The Use of Error Functions for Validation of Isotherm and Kinetics Models.

PubMed

Rahman, Md Sayedur; Sathasivam, Kathiresan V

2015-01-01

Biosorption process is a promising technology for the removal of heavy metals from industrial wastes and effluents using low-cost and effective biosorbents. In the present study, adsorption of Pb(2+), Cu(2+), Fe(2+), and Zn(2+) onto dried biomass of red seaweed Kappaphycus sp. was investigated as a function of pH, contact time, initial metal ion concentration, and temperature. The experimental data were evaluated by four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) and four kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models). The adsorption process was feasible, spontaneous, and endothermic in nature. Functional groups in the biomass involved in metal adsorption process were revealed as carboxylic and sulfonic acids and sulfonate by Fourier transform infrared analysis. A total of nine error functions were applied to validate the models. We strongly suggest the analysis of error functions for validating adsorption isotherm and kinetic models using linear methods. The present work shows that the red seaweed Kappaphycus sp. can be used as a potentially low-cost biosorbent for the removal of heavy metal ions from aqueous solutions. Further study is warranted to evaluate its feasibility for the removal of heavy metals from the real environment.

[Copper recovery from artificial bioleaching lixivium of waste printed circuit boards].

PubMed

Cheng, Dan; Zhu, Neng-Wu; Wu, Ping-Xiao; Zou, Ding-Hui; Xing, Yi-Jia

2014-04-01

The key step to realize metal recovery from bioleaching solutions is the recovery of copper from bioleaching lixivium of waste printed circuit boards in high-grade form. The influences of cathode material, current density, initial pH and initial copper ion concentration on the efficiency and energy consumption of copper recovery from artificial bioleaching lixivium under condition of constant current were investigated using an electro-deposition approach. The results showed that the larger specific surface area of the cathode material (carbon felt) led to the higher copper recovery efficiency (the recovery efficiencies of the anode and the cathode chambers were 96.56% and 99.25%, respectively) and the smaller the total and unit mass product energy consumption (the total and unit mass product energy consumptions were 0.022 kW x h and 15.71 kW x h x kg(-1), respectively). The copper recovery efficiency and energy consumption increased with the increase of current density. When the current density was 155.56 mA x cm(-2), the highest copper recovery efficiencies in the anode and cathode chambers reached 98.51% and 99.37%, respectively. Accordingly, the highest total and unit mass product energy consumptions were 0.037 kW x h and 24.34 kW x h x kg(-1), respectively. The copper recovery efficiency was also significantly affected by the initial copper ion concentration. The increase of the initial copper ion concentration would lead to faster decrease of copper ion concentration, higher total energy consumption, and lower unit mass product consumption. However, the initial pH had no significant effect on the copper recovery efficiency. Under the optimal conditions (carbon felt for cathode materials, current density of 111.11 mA x cm(-2), initial pH of 2.0, and initial copper ion concentration of 10 g x L(-1)), the copper recovery efficiencies of the anode and cathode chambers were 96.75% and 99.35%, and the total and unit mass product energy consumptions were 0.021 kW x h and 14.61 kW x h x kg(-1), respectively. The deposited copper on the cathode material was fascicularly distributed and no oxygen was detected.

Effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13

DOE Office of Scientific and Technical Information (OSTI.GOV)

John E. Aston; William A. Apel; Brady D. Lee

2010-12-01

This study describes the effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13 with a Langmuir model. Copper exhibited the highest loading capacity, 4.76 ± 0.28 mmol g-1, to viable cells at pH 5.5. The highest kL (binding-site affinity) observed was 61.2 ± 3.0 L mmol-1 to dehydrated cells at pH 4.0. The pHs that maximized loading capacities and binding-site affinities were generally between 4.0 and 5.5, where the sum of free-proton and complexed-metal concentrations was near a minimum. Of additional importance, lead, zinc, and copper sorbed to viable cells atmore » pH values as low as 1.5. Previous studies with other acidithiobacilli did not measure viable-cell sorption below pH 4.0. In separate experiments, desorption studies showed that far less copper was recovered from viable cells than any other metal or cell condition, suggesting that uptake may play an important role in copper sorption by At. caldus strain BC13. To reflect an applied system, the sorption of metal mixtures was also studied. In these experiments, lead, zinc, and copper sorption from a tertiary mixture were 40.2 ± 4.3%, 28.7 ± 3.8%, and 91.3 ± 3.0%, respectively, of that sorbed in single-metal systems.« less

Comparison of nickel biosorption properties of living and dead Rhizopus arrhizus biosorbent

NASA Astrophysics Data System (ADS)

Silah, Hülya; Gül, Ülküye Dudu

2017-04-01

The passive removal of commonly used heavy metal Ni(II), from aqueous solutions by inexpensive biomaterial, fungi Rhizopus arrhizus biomass, termed biosorption, was studied in this study. The effects of biomass type (living and dead) and pH (2-6) on metal removal by fungus were investigated. The dead biomass (44.2%) exhibited higher uptake ability of Ni(II) than living biomass (40.5%) at 100 mg/L heavy metal after 6 h. Optimal pH for biosorption was 6.

Temporal evolution of bacterial communities associated with the in situ wetland-based remediation of a marine shore porphyry copper tailings deposit.

PubMed

Diaby, N; Dold, B; Rohrbach, E; Holliger, C; Rossi, P

2015-11-15

Mine tailings are a serious threat to the environment and public health. Remediation of these residues can be carried out effectively by the activation of specific microbial processes. This article presents detailed information about temporal changes in bacterial community composition during the remediation of a section of porphyry copper tailings deposited on the Bahía de Ite shoreline (Peru). An experimental remediation cell was flooded and transformed into a wetland in order to prevent oxidation processes, immobilizing metals. Initially, the top oxidation zone of the tailings deposit displayed a low pH (3.1) and high concentrations of metals, sulfate, and chloride, in a sandy grain size geological matrix. This habitat was dominated by sulfur- and iron-oxidizing bacteria, such as Leptospirillum spp., Acidithiobacillus spp., and Sulfobacillus spp., in a microbial community which structure resembled acid mine drainage environments. After wetland implementation, the cell was water-saturated, the acidity was consumed and metals dropped to a fraction of their initial respective concentrations. Bacterial communities analyzed by massive sequencing showed time-dependent changes both in composition and cell numbers. The final remediation stage was characterized by the highest bacterial diversity and evenness. Aside from classical sulfate reducers from the phyla δ-Proteobacteria and Firmicutes, community structure comprised taxa derived from very diverse habitats. The community was also characterized by an elevated proportion of rare phyla and unaffiliated sequences. Numerical ecology analysis confirmed that the temporal population evolution was driven by pH, redox, and K. Results of this study demonstrated the usefulness of a detailed follow-up of the remediation process, not only for the elucidation of the communities gradually switching from autotrophic, oxidizing to heterotrophic and reducing living conditions, but also for the long term management of the remediation wetlands. Copyright © 2015 Elsevier B.V. All rights reserved.

Metal binding stoichiometry and isotherm choice in biosorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schiewer, S.; Wong, M.H.

1999-11-01

Seaweeds that possess a high metal binding capacity may be used as biosorbents for the removal of toxic heavy metals from wastewater. The binding of Cu and Ni by three brown algae (Sargassum, Colpomenia, Petalonia) and one green alga (Ulva) was investigated at pH 4.0 and pH 3.0. The greater binding strength of Cu is reflected in a binding constant that is about 10 times as high as that of Ni. The extent of metal binding followed the order Petalonia {approximately} Sargassum > Colpomenia > Ulva. This was caused by a decreasing number of binding sites and by much lowermore » metal binding constants for Ulva as compared to the brown algae. Three different stoichiometric assumptions are compared for describing the metal binding, which assume either that each metal ion M binds to one binding site B forming a BM complex or that a divalent metal ion M binds to two monovalent sites B forming BM{sub 0.5} or B{sub 2}M complexes, respectively. Stoichiometry plots are proposed as tools to discern the relevant binding stoichiometry. The pH effect in metal binding and the change in proton binding were well predicted for the B{sub 2}M or BM{sub 0.5} stoichiometries with the former being better for Cu and the latter preferable for Ni. Overall, the BM{sub 0.5} model is recommended because it avoids iterations.« less

Magnetic-epichlorohydrin crosslinked chitosan schiff's base (m-ECCSB) as a novel adsorbent for the removal of Cu(II) ions from aqueous environment.

PubMed

Gutha, Yuvaraja; Zhang, Yaping; Zhang, Weijiang; Jiao, Xu

2017-04-01

Metal ions cause a serious public health problem. It is a great challenge to find an effective and efficient adsorbent to remove heavy metals from wastewater. Chitosan-based adsorbents are potential and effective for heavy metal ion removal. Hence a novel m-ECCSB was synthesized, characterized and utilized as an adsorbent for the removal of Cu(II) ions from aqueous solution. Various factors affecting the uptake behavior such as pH, adsorbent dosage, contact time, initial concentration of Cu(II) and temperature effect were investigated. Maximum adsorption capability (123.10mg/g) was obtained at pH=6, adsorbent dose of=250mg, rotational speed=200rpm, contact time=60min, and temperature of 323K. The result of the kinetic study shows that the adsorption of Cu(II) could be described by the pseudo-second-order equation. Equilibrium data were analysed with the Langmuir, Freundlich and Dubinin-Radushkevich isotherms and Langmuir model was found to provide the best fit of the experimental data. The thermodynamic parameters showed that the adsorption of Cu(II) onto m-ECCSB was spontaneous (ΔG°=-8.990, -10.00 and -10.593kJ/mol), endothermic (ΔH°=15.674, 15.478 and 15.699kJ/mol) and ΔS° (0.0814J/molK) suggests an increased randomness at the solid/solution interface under the studied conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Acidithiobacillus ferrooxidans metabolism: from genome sequence to industrial applications.

PubMed

Valdés, Jorge; Pedroso, Inti; Quatrini, Raquel; Dodson, Robert J; Tettelin, Herve; Blake, Robert; Eisen, Jonathan A; Holmes, David S

2008-12-11

Acidithiobacillus ferrooxidans is a major participant in consortia of microorganisms used for the industrial recovery of copper (bioleaching or biomining). It is a chemolithoautrophic, gamma-proteobacterium using energy from the oxidation of iron- and sulfur-containing minerals for growth. It thrives at extremely low pH (pH 1-2) and fixes both carbon and nitrogen from the atmosphere. It solubilizes copper and other metals from rocks and plays an important role in nutrient and metal biogeochemical cycling in acid environments. The lack of a well-developed system for genetic manipulation has prevented thorough exploration of its physiology. Also, confusion has been caused by prior metabolic models constructed based upon the examination of multiple, and sometimes distantly related, strains of the microorganism. The genome of the type strain A. ferrooxidans ATCC 23270 was sequenced and annotated to identify general features and provide a framework for in silico metabolic reconstruction. Earlier models of iron and sulfur oxidation, biofilm formation, quorum sensing, inorganic ion uptake, and amino acid metabolism are confirmed and extended. Initial models are presented for central carbon metabolism, anaerobic metabolism (including sulfur reduction, hydrogen metabolism and nitrogen fixation), stress responses, DNA repair, and metal and toxic compound fluxes. Bioinformatics analysis provides a valuable platform for gene discovery and functional prediction that helps explain the activity of A. ferrooxidans in industrial bioleaching and its role as a primary producer in acidic environments. An analysis of the genome of the type strain provides a coherent view of its gene content and metabolic potential.

Immobilizer-assisted management of metal-contaminated agricultural soils for safer food production.

PubMed

Kim, Kwon-Rae; Kim, Jeong-Gyu; Park, Jeong-Sik; Kim, Min-Suk; Owens, Gary; Youn, Gyu-Hoon; Lee, Jin-Su

2012-07-15

Production of food crops on metal contaminated agricultural soils is of concern because consumers are potentially exposed to hazardous metals via dietary intake of such crops or crop derived products. Therefore, the current study was conducted to develop management protocols for crop cultivation to allow safer food production. Metal uptake, as influenced by pH change-induced immobilizing agents (dolomite, steel slag, and agricultural lime) and sorption agents (zeolite and compost), was monitored in three common plants representative of leafy (Chinese cabbage), root (spring onion) and fruit (red pepper) vegetables, in a field experiment. The efficiency of the immobilizing agents was assessed by their ability to decrease the phytoavailability of metals (Cd, Pb, and Zn). The fruit vegetable (red pepper) showed the least accumulation of Cd (0.16-0.29 mgkg(-1) DW) and Pb (0.2-0.9 mgkg(-1) DW) in edible parts regardless of treatment, indicating selection of low metal accumulating crops was a reasonable strategy for safer food production. However, safer food production was more likely to be achievable by combining crop selection with immobilizing agent amendment of soils. Among the immobilizing agents, pH change-induced immobilizers were more effective than sorption agents, showing decreases in Cd and Pb concentrations in each plant well below standard limits. The efficiency of pH change-induced immobilizers was also comparable to reductions obtained by 'clean soil cover' where the total metal concentrations of the plow layer was reduced via capping the surface with uncontaminated soil, implying that pH change-induced immobilizers can be practically applied to metal contaminated agricultural soils for safer food production. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of acidification on metal accumulation by aquatic plants and invertebrates. 1. Constructed wetlands

USGS Publications Warehouse

Albers, P.H.; Camardese, M.B.

1993-01-01

The pH of lake water is often inversely correlated with concentrations of trace metals in the water column. Concentrations of Al, Cd, Ca, Cu, Fe, Hg, Pb, Mg, Mn, Ni, P, and Zn were compared in water, plants, and aquatic insects from three acidified (pH 5.0) and three nonacidified (pH 6.5) constructed wetlands. Concentrations of Zn in water and bur-reed (Sparganium americanum) were higher in acidified wetlands than in nonacidified wetlands. Floating nonrooted plants contained mean concentrations of Fe, Mg, and Mn that were higher than recommended maximum levels for poultry feed. The mean concentrations of all metals in insects were below recommended maximum levels for poultry feed and below levels that cause toxic effects in wild birds. Smaller than expected increases of metal concentrations in the water of acidified wetlands were probably due to limited mobilization of metals from the sediments and insignificant changes in sedimentation of aqueous metals. Calcium was lower in acidified than in nonacidified wetland water, but the Ca content of insects and bur-reed was not lower. Low concentrations of Ca in aquatic insects from both groups of wetlands indicate that calcium-rich crustaceans and mollusks are probably important to female waterfowl and their young during the spring, when invertebrates make up the majority of the diet. Although toxic effects from metal ingestion seem to be unlikely consequences of wetland acidification, the adverse effect of low pH on the occurrence of crustaceans and mollusks could threaten egg production and development of young.

XAFS studies of metal-ligand interactions at organic surfaces and in solution

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.

X-ray absorption fine structure spectroscopy (XAFS) was used as a structural probe to determine the mechanism of metal adsorption to organic surfaces. Two specific systems were investigated, Pb adsorption to heneicosanoic acid Langmuir monolayers (CH3(CH2)19COOH), and Cd adsorption to isolated cell walls of the Bacillus subtilis bacterium. Although the study of these systems is important for quite different reasons, the goal in both is metal binding site speciation and structural characterization of the surface complex. The adsorption of aqueous Cd to B. subtilis was studied as a function of pH by fluorescence mode bulk XAFS. Samples were prepared at six pH values in the range 3.4 to 7.8, and the bacterial functional groups responsible for the adsorption were identified under each condition. Under the experimental Cd and bacterial concentrations, the spectroscopy results indicate that Cd binds predominantly to protonated phosphoryl ligands below pH 4.4, while at higher pH adsorption to carboxyl groups becomes increasingly important. At pH 7.8 we observe the activation of an additional binding site, which we tentatively ascribe to deprotonated phosphoryl ligands. A quantitative Cd speciation diagram for the pH range is presented. Grazing-incidence Pb L3 edge XAFS was used in situ to determine the adsorption complex structure in the Pb-Langmuir monolayer study. The results indicate covalent binding of the Pb cations to the carboxyl headgroups, and the observed Pb-Pb coordination suggests that the metal is adsorbed as a hydrolysis polymer, rather than as individual Pb 2+ ions. The data suggest a bidentate binding mechanism and a one Pb atom to one carboxyl headgroup binding stoichiometry. We discuss how this adsorption model can explain the peculiarities observed with Pb in previous metal-Langmuir monolayer studies. A systematic study of the metal local environment in aqueous solutions was conducted and used in the above analyses. Perchlorate and acetate salt solutions of Cd, Pb, Mn, Cr, and Cu were characterized as standards of hydrated ions and metal-carboxyl complexes. The utility of XAFS in differentiating between the ionic, monodentate, bridging-bidentate, and bidentate metal-carboxyl complexes through C-C multiple scattering effects and XANES features is demonstrated.

Linking Mn(II)-oxidizing bacteria to natural attenuation at a former U mining site

NASA Astrophysics Data System (ADS)

Akob, D.; Bohu, T.; Beyer, A.; Schäffner, F.; Händel, M.; Johnson, C.; Merten, D.; Büchel, G.; Totsche, K.; Küsel, K.

2012-04-01

Uranium mining near Ronneburg, Germany resulted in widespread environmental contamination with acid mine drainage (AMD) and high concentrations of heavy metals and radionuclides. Despite physical remediation of the area, groundwater is still a source of heavy metal contaminants, e.g., Cd, Ni, Co, Cu and Zn, to nearby ecosystems. However, natural attenuation of heavy metals is occurring in Mn oxide rich soils and sediments ranging in pH from 5 to 7. While microorganisms readily oxidize Mn(II) and precipitate Mn oxides at pH ~7 under oxic conditions, few studies describe Mn(II)-oxidizing bacteria (MOB) at pH ~5 and/or in the presence of heavy metals. In this study we (1) isolated MOB from the contaminated Ronneburg area at pH 5.5 and 7 and (2) evaluated the biological formation of Mn oxides. We isolated nine MOB strains at pH 7 (members of the Proteobacteria, Actinobacteria, Bacteroidetes, and Firmicutes phyla) and a single isolate at pH 5.5 (Oxalobacteraceae isolate AB_14, within the β-Proteobacteria). LA-ICP-MS showed that all isolates accumulated Mn and Fe in their biomass. However, the Oxalobacteraceae isolate AB_14 oxidizes more Mn without additional Fe in the medium. Preliminary FTIR analysis indicated that all isolates formed precipitates, which showed absorption bands that were characteristic for birnessite. High resolution TEM showed variable morphology of precipitates and EDS confirmed the presence of Mn oxides. Isolate AB_14 was not surrounded with precipitates whereas our Actinobacteria isolate AB_18 was encrusted with Mn oxides. Electron diffraction is currently being used to confirm the presence of birnessite and other Mn oxide phases. This, the first known report of any organism capable of Mn oxidation at low pH, demonstrated that MOB can be involved in the natural attenuation of both moderately acidic and neutral pH soils and sediments via the formation of biogenic Mn oxides. Future work will fully evaluate the minerals formed in this process as well as their interactions with contaminating heavy metals and radionuclides.

Wash Solution Bath Life Extension for the Space Shuttle Rocket Motor Aqueous Cleaning System

NASA Technical Reports Server (NTRS)

Saunders, Chad; Evans, Kurt; Sagers, Neil

1999-01-01

A spray-in-air aqueous cleaning system, which replaced 1,1,1 trichloroethane (TCA) vapor degreasing, is used for critical cleaning of Space Shuttle Redesigned Solid Rocket Motor (RSRM) metal parts. Small-scale testing demonstrated that the alkaline-based wash solution possesses adequate soil loading and cleaning properties. However, full-scale testing exhibited unexpected depletion of some primary components of the wash solution. Specifically, there was a significant decrease in the concentration of sodium metasilicate which forced change-out of the wash solution after eight days. Extension of wash solution bath life was necessary to ease the burden of frequent change-out on manufacturing. A laboratory study supports a depletion mechanism that is initiated by the hydrolysis of sodium tripolyphosphate (STPP) lowering the pH of the solution. The decrease in pH causes polymerization and subsequent precipitation of sodium metasilicate (SM). Further investigation showed that maintaining the pH was the key to preventing the precipitation of the sodium metasilicate. Implementation to the full scale operation demonstrated that periodic additions of potassium hydroxide (KOH) extended the useful bath life to more than four months.

Fungal trehalose phosphorylase: kinetic mechanism, pH-dependence of the reaction and some structural properties of the enzyme from Schizophyllum commune.

PubMed Central

Eis, C; Watkins, M; Prohaska, T; Nidetzky, B

2001-01-01

Initial-velocity measurements for the phospholysis and synthesis of alpha,alpha-trehalose catalysed by trehalose phosphorylase from Schizophyllum commune and product and dead-end inhibitor studies show that this enzyme has an ordered Bi Bi kinetic mechanism, in which phosphate binds before alpha,alpha-trehalose, and alpha-D-glucose is released before alpha-D-glucose 1-phosphate. The free-energy profile for the enzymic reaction at physiological reactant concentrations displays its largest barriers for steps involved in reverse glucosyl transfer to D-glucose, and reveals the direction of phospholysis to be favoured thermodynamically. The pH dependence of kinetic parameters for all substrates and the dissociation constant of D-glucal, a competitive dead-end inhibitor against D-glucose (K(i)=0.3 mM at pH 6.6 and 30 degrees C), were determined. Maximum velocities and catalytic efficiencies for the forward and reverse reactions decrease at high and low pH, giving apparent pK values of 7.2--7.8 and 5.5--6.0 for two groups whose correct protonation state is required for catalysis. The pH dependences of k(cat)/K are interpreted in terms of monoanionic phosphate and alpha-D-glucose 1-phosphate being the substrates, and of the pK value seen at high pH corresponding to the phosphate group in solution or bound to the enzyme. The K(i) value for the inhibitor decreases outside the optimum pH range for catalysis, indicating that binding of D-glucal is tighter with incorrectly ionized forms of the complex between the enzyme and alpha-D-glucose 1-phosphate. Each molecule of trehalose phosphorylase contains one Mg(2+) that is non-dissociable in the presence of metal chelators. Measurements of the (26)Mg(2+)/(24)Mg(2+) ratio in the solvent and on the enzyme by using inductively coupled plasma MS show that exchange of metal ion between protein and solution does not occur at measurable rates. Tryptic peptide mass mapping reveals close structural similarity between trehalose phosphorylases from basidiomycete fungi. PMID:11389683

Cadmium and Zn availability as affected by pH manipulation and its assessment by soil extraction, DGT and indicator plants.

PubMed

Muhammad, Iqbal; Puschenreiter, Markus; Wenzel, Walter W

2012-02-01

Manipulation of soil pH by soil additives and / or rhizosphere processes may enhance the efficiency of metal phytoextraction. Here we report on the effect of nitric acid additions to four polluted soils on Cd and Zn concentrations in soil solution (C(soln)) and 0.005M Ca(NO(3))(2) extracts, and related changes in the diffusive fluxes and resupply of the metals as assessed by diffusive gradients in thin films (DGT). The responses of these chemical indicators of bioavailability were compared to metal uptake in two indicator plant species, common dandelion (Taraxacum officinale F.H. Wigg) and narrow leaf plantain (Plantago lanceolata L.) grown for 75days in a pot experiment. Lowering soil pH increased C(soln), the 0.005M Ca(NO(3))(2)-soluble fractions and the DGT-measured Cd and Zn concentrations (C(DGT)) in the experimental soils. This was associated with enhanced uptake of Cd and Zn on soils acidified to pH 4.5 whereas plants did not survive at pH 3.5. Toxicity along with decreased kinetics of metal resupply (calculated by the 2D DIFS model) in the strong acidification treatment suggests that moderate acidification is more appropriate to enhance the phytoextraction process. Each of the chemical indicators of bioavailability predicted well (R(2)>0.70) the Cd and Zn concentrations in plantain shoots but due to metal toxicity not for dandelion. Concentration factors, i.e. the ratio between metal concentrations in shoots and in soil solution (CF) indicate that Cd and Zn uptake in plantain was not limited by diffusion which may explain that DGT did not perform better than C(soln). However, DGT is expected to predict plant uptake better in diffusion-limited conditions such as in the rhizosphere of metal-accumulating phytoextraction crops. Copyright © 2011 Elsevier B.V. All rights reserved.

Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

PubMed

Kitadai, Norio

2017-03-01

Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg 2+ ) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu 2+ ) are therefore not beneficial places for peptide bond formation on the primitive Earth.

Comprehensive reuse of drinking water treatment residuals in coagulation and adsorption processes.

PubMed

Jung, Kyung-Won; Hwang, Min-Jin; Park, Dae-Seon; Ahn, Kyu-Hong

2016-10-01

While drinking water treatment residuals (DWTRs) inevitably lead to serious problems due to their huge amount of generation and limitation of landfill sites, their unique properties of containing Al or Fe contents make it possible to reuse them as a beneficial material for coagulant recovery and adsorbent. Hence, in the present study, to comprehensively handle and recycle DWTRs, coagulant recovery from DWTRs and reuse of coagulant recovered residuals (CRs) were investigated. In the first step, coagulant recovery from DWTRs was conducted using response surface methodology (RSM) for statistical optimization of independent variables (pH, solid content, and reaction time) on response variable (Al recovery). As a result, a highly acceptable Al recovery of 97.5 ± 0.4% was recorded, which corresponds to 99.5% of the predicted Al recovery. Comparison study of recovered and commercial coagulant from textile wastewater treatment indicated that recovered coagulant has reasonable potential for use in wastewater treatment, in which the performance efficiencies were 68.5 ± 2.1% COD, 97.2 ± 1.9% turbidity, and 64.3 ± 1.0% color removals at 50 mg Al/L. Subsequently, in a similar manner, RSM was also applied to optimize coagulation conditions (Al dosage, initial pH, and reaction time) for the maximization of real cotton textile wastewater treatment in terms of COD, turbidity, and color removal. Overall performance revealed that the initial pH had a remarkable effect on the removal performance compared to the effects of other independent variables. This is mainly due to the transformation of metal species form with increasing or decreasing pH conditions. Finally, a feasibility test of CRs as adsorbent for phosphate adsorption from aqueous solution was conducted. Adsorption equilibrium of phosphate at different temperatures (10-30 °C) and initial levels of pH (3-11) indicated that the main mechanisms of phosphate adsorption onto CRs are endothermic and chemical precipitation; the surfaces are energetically heterogeneous for adsorbing phosphate. Copyright © 2016 Elsevier Ltd. All rights reserved.

The remediation of heavy metals contaminated sediment.

PubMed

Peng, Jian-Feng; Song, Yong-Hui; Yuan, Peng; Cui, Xiao-Yu; Qiu, Guang-Lei

2009-01-30

Heavy metal contamination has become a worldwide problem through disturbing the normal functions of rivers and lakes. Sediment, as the largest storage and resources of heavy metal, plays a rather important role in metal transformations. This paper provides a review on the geochemical forms, affecting factors and remediation technologies of heavy metal in sediment. The in situ remediation of sediment aims at increasing the stabilization of some metals such as the mobile and the exchangeable fractions; whereas, the ex situ remediation mainly aims at removing those potentially mobile metals, such as the Mn-oxides and the organic matter (OM) fraction. The pH and OM can directly change metals distribution in sediment; however oxidation-reduction potential (ORP), mainly through changing the pH values, indirectly alters metals distribution. Mainly ascribed to their simple operation mode, low costs and fast remediation effects, in situ remediation technologies, especially being fit for slight pollution sediment, are applied widely. However, for avoiding metal secondary pollution from sediment release, ex situ remediation should be the hot point in future research.

Metal resistance or tolerance? Acidophiles confront high metal loads via both abiotic and biotic mechanisms.

PubMed

Dopson, Mark; Ossandon, Francisco J; Lövgren, Lars; Holmes, David S

2014-01-01

All metals are toxic at high concentrations and consequently their intracellular concentrations must be regulated. Extremely acidophilic microorganisms have an optimum growth of pH <3 and proliferate in natural and anthropogenic low pH environments. Some acidophiles are involved in the catalysis of sulfide mineral dissolution, resulting in high concentrations of metals in solution. Acidophiles are often described as highly metal resistant via mechanisms such as multiple and/or more efficient active resistance systems than are present in neutrophiles. However, this is not the case for all acidophiles and we contend that their growth in high metal concentrations is partially due to an intrinsic tolerance as a consequence of the environment in which they live. In this perspective, we highlight metal tolerance via complexation of free metals by sulfate ions and passive tolerance to metal influx via an internal positive cytoplasmic transmembrane potential. These tolerance mechanisms have been largely ignored in past studies of acidophile growth in the presence of metals and should be taken into account.

Rapid Computer Aided Ligand Design and Screening of Precious Metal Extractants from TRUEX Raffinate with Experimental Validation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, Aurora Sue; Wall, Nathalie; Benny, Paul

2015-11-16

Rhodium is the most extensively used metal in catalytic applications; it occurs in mixed ores with platinum group metals (PGMs) in the earth’s crust in low concentrations (0.4 - 10 ppb). It is resistant to aerial oxidation and insoluble in all acids, including aqua regia, making classical purification methods time-consuming and inefficient. To ensure adequate purity, several precipitation and dissolution steps are necessary during separation. Low abundance, high demand, and extensive processing make rhodium the most expensive of all PGMs. From alternative sources, rhodium is also produced in sufficient quantities (0.47 kg per ton initial heavy metal (tIHM)) during themore » fission of U-235 in nuclear reactors along with other PGMs (i.e., Ag, Pd, Ru). A typical power water reactor operating with UO 2 fuel after cooling can generate PGMs in quantities greater than found in the earth’s crust (0.5-2 kg/tIHM). This currently untapped supply of PGMs has the potential to yield $5,000-30,000/tIHM. It is estimated that by the year 2030, the amount of rhodium generated in reactors could exceed natural reserves. Typical SNF processing removes the heavier lanthanides and actinides and can leave PGMs at ambient temperatures in aqueous acidic (Cl⁻ or NO 3⁻; pH < 1) solutions at various activities. While the retrieval of these precious metals from SNF would minimize waste generation and improve resource utilization, it has been difficult to achieve thus far. Two general strategies have been utilized to extract Rh(III) from chloride media: ion pairing and coordination complexation. Ion pairing mechanisms have been studied primarily with the tertiary and quaternary amines. Additionally, mixed mechanism extractions have been observed in which ion pairing is the initial mechanism, and longer extraction equilibrium time generated coordination complexes. Very few coordination complexation extraction ligands have been studied. This project approached this problem through the design of a software program that uses state-of-the-art computational combinatorial chemistry, and is developed and validated with experimental data acquisition; the resulting tool allows for rapid design and screening of new ligands for the extraction of precious metals from SNF. This document describes the software that has been produced, ligands that have been designed, and fundamental new understandings of the extraction process of Rh(III) as a function of solution phase conditions (pH, nature of acid, etc.).« less

Accumulation of metal ions by pectinates

NASA Astrophysics Data System (ADS)

Deiana, S.; Deiana, L.; Palma, A.; Premoli, A.; Senette, C.

2009-04-01

The knowledge of the mechanisms which regulate the interactions of metal ions with partially methyl esterified linear polymers of α-1,4 linked D-galacturonic acid units (pectinates), well represented in the root inner and outer apoplasm, is of great relevance to understand the processes which control their accumulation at the soil-root interface as well as their mobilization by plant metabolites. Accumulation of a metal by pectinates can be affected by the presence of other metals so that competition or distribution could be expected depending on the similar or different affinity of the metal ions towards the binding sites, mainly represented by the carboxylate groups. In order to better understand the mechanism of accumulation in the apoplasm of several metal ions, the sorption of Cd(II), Zn(II), Cu(II), Pb(II) and Cr(III) by a Ca-polygalacturonate gel, used as model of the soil-root interface, with a degree of esterification of 18% (PGAE1) and 65% (PGAE2) was studied at pH 3.0, 4.0, 5.0 and 6.0 in the presence of CaCl2 2.5 mM.. The results show that sorption increases with increasing both the initial metal concentration and pH. A similar sorption trend was evidenced for Cu(II) and Pb(II) and for Zn(II) and Cd(II), indicating that the mechanism of sorption for these two ionic couples is quite different. As an example, at pH 6.0 and an initial metal concentration equal to 2.0 mM, the amount of Cu(II) and Pb(II) sorbed was about 1.98 mg-1 of PGAE1 while that of Cd(II) and Zn(II) was about 1.2 mg-1. Cr(III) showed a rather different sorption trend and a much higher amount (2.8 mg-1of PGAE1 at pH 6.0) was recorded. The higher affinity of Cr(III) for the polysaccharidic matrix is attributable to the formation of Cr(III) polynuclear species in solution, as shown by the distribution diagrams obtained through the MEDUSA software. On the basis of these findings, the following affinity towards the PGAE1 can be assessed: Cr(III) > Cu(II) ? Pb(II) > Zn (II) ? Cd(II). Surprisingly, simultaneous sorption tests and SEM analyses indicate that a different mechanism regulates the sorption of Cu(II) and Pb(II) by PGAE1. In fact, the amount of Pb(II) sorbed (0.92 moles mg-1of PGAE1) by PGAE1 was nearly independent by the presence of Cu(II) ions, at least at the three different concentrations tested, that indicates a higher affinity of Pb(II). Such an aspect was further confirmed by exchange experiments. Samples of PGAE1 saturated with 1.96 moles mg-1of Cu(II) or 2.01 moles mg-1of Pb(II) were put in contact with 100 mL of solutions containing 97.3 moles of Pb(II) or 99.4 moles Cu(II), respectively. The exchange kinetics show that about 80% of Cu(II) was stochiometrically exchanged by Pb(II). In contrast, only about 10% of Pb(II) complexed by PGAE1 was exchanged by Cu(II). The kinetics of simultaneous sorption of all the metal ions tested indicate that Pb(II) is selectively sorbed by the PGAE1 gels. Cd(II) and Zn(II) show a similar affinity towards PGAE1. Thus, in the simultaneous presence of these ions, their selectivity towards this matrix follows the order: Pb > Cu > Cd ? Zn. Sorption of Cr(III) in the presence of the ions considered was not possible to carry out due to interference phenomena. The sorption of the same ions by 50 mg of PGAE2 evidences that the amount of Cu(II), Pb(II), and Cr(III) sorbed is markedly lower than that found for PGAE1. By considering that two carboxylic groups are involved in the complexation of a metal ion, the data show that such a stoichiometry is respected only for Pb(II). The amount of Cu(II) sorbed is about 50% lower than that of Pb(II) at all the pH values tested whereas those of Zn(II) and Cd(II) are negligible whereas that of Cr(III) is the highest. The different behaviour of Cu(II) compared to Pb(II) can be explained taking into account for both hydrophobic and steric effects of the methyl groups as well as to their different charge density. Thus, it can be concluded that the accumulation of metals at the soil-root interface strictly depends on the esterification degree of the root pectinates which, even highly esterified, do not loose the ability to accumulate metals, mainly Pb(II) and Cr(III).

Photodegradation of Acid Violet 7 with AgBr-ZnO under highly alkaline conditions.

PubMed

Krishnakumar, B; Swaminathan, M

2012-12-01

The photocatalytic activity of AgBr-ZnO was investigated for the degradation of Acid Violet 7 (AV 7) in aqueous solution using UV-A light. AgBr-ZnO is found to be more efficient than commercial ZnO and prepared ZnO at pH 12 for the mineralization of AV 7. The effects of operational parameters such as the amount of photocatalyst, dye concentration, initial pH on photo mineralization have been analyzed. Expect oxone, other oxidants decrease the degradation efficiency. Addition of metal ions and anions decrease the degradation efficiency of AgBr-ZnO significantly. The mineralization of AV 7 has also been confirmed by COD measurements. The mechanism of degradation by AgBr-ZnO is proposed to explain its higher activity under UV light. The catalyst is found to be reusable. Copyright © 2012 Elsevier B.V. All rights reserved.

Corrosion control in water supply systems: effect of pH, alkalinity, and orthophosphate on lead and copper leaching from brass plumbing.

PubMed

Tam, Y S; Elefsiniotis, P

2009-10-01

This study explored the potential of lead and copper leaching from brass plumbing in the Auckland region of New Zealand. A five-month field investigation, at six representative locations, indicated that Auckland's water can be characterized as soft and potentially corrosive, having low alkalinity and hardness levels and a moderately alkaline pH. More than 90% of the unflushed samples contained lead above the maximum acceptable value (MAV) of 10 microg/L (New Zealand Standards). In contrast, the copper level of unflushed samples remained consistently below the corresponding MAV of 2 mg/L. Flushing however reduced sharply metal concentrations, with lead values well below the MAV limit. Generally, metal leaching patterns showed a limited degree of correlation with the variations in temperature, dissolved oxygen and free chlorine residual at all sampling locations. Furthermore, a series of bench-scale experiments was conducted to evaluate the effectiveness of pH and alkalinity adjustment, as well as orthophosphate addition as corrosion control tools regarding lead and copper dissolution. Results demonstrated that lead and copper leaching was predominant during the first 24 hr of stagnation, but reached an equilibrium state afterwards. Since the soluble fraction of both metals was small (12% for lead, 29% for copper), it is apparent that the non-soluble compounds play a predominant role in the dissolution process. The degree of leaching however was largely affected by the variations in pH and alkalinity. At pH around neutrality, an increase in alkalinity promoted metal dissolution, while at pH 9.0 the effect of alkalinity on leaching was marginal. Lastly, addition of orthophosphate as a corrosion inhibitor was more effective at pH 7.5 or higher, resulting in approximately 70% reduction in both lead and copper concentrations.

Mechanistic characterization of the HDV genomic ribozyme: a mutant of the C41 motif provides insight into the positioning and thermodynamic linkage of metal ions and protons.

PubMed

Nakano, Shu-ichi; Bevilacqua, Philip C

2007-03-20

Binding of two Mg2+ and two H+ ions influences the self-cleavage activity of the genomic HDV ribozyme. The positioning of these four ligands and their thermodynamic linkage are not fully resolved. Protonated C41 engages in a base triple, whereas protonated C75 has been implicated as an acid-base catalyst in bond cleavage. Prior studies led to the identification of one structural inner-sphere ion and one catalytic outer-sphere ion. In the present study, the contributions of the C41 base triple to the metal ion- and pH-dependence of the reaction are examined. Experiments were conducted on a CG to UA double mutant (DM), which changes the base triple to one involving an unprotonated C41. Below pH 6, the DM has a steeper dependence on pH than the wild-type (WT), consistent with a single protonation misfolding the core; this conclusion is also supported by thermal denaturation studies. Between pH 6 and 8, the WT and DM display nearly identical catalytic metal ion and H+ binding profiles. In contrast, over the same pH range, the WT and DM have distinct structural ion binding profiles; for the WT, binding is favored at lower pH, whereas the DM shows no pH dependence. These data localize the structural ion to the vicinity of the C41 motif. An overall model is presented that accommodates binding affinity, coupling, and positioning of the two metal ions and the two protons within the ribozyme. The data suggest that a protonated base triple allows the WT ribozyme to maintain appreciable activity at acidic pH, which could play an important role in the life cycle of the virus.

Electroneutral, HCO3(-)-independent, pH gradient-dependent uphill transport of Cl- by ileal brush-border membrane vesicles. Possible role in the pathogenesis of chloridorrhea.

PubMed Central

Vasseur, M; Caüzac, M; Alvarado, F

1989-01-01

By applying a rapid filtration technique to isolated brush border membrane vesicles from guinea pig ileum, 36Cl uptake was quantified in the presence and absence of electrical, pH and alkali-metal ion gradients. A mixture of 20 mM-Hepes and 40 mM-citric acid, adjusted to the desired pH with Tris base, was found to be the most suitable buffer. Malate and Mes could be used to replace the citrate, but succinate, acetate and maleate proved to be unsuitable. In the absence of a pH gradient (pHout:pHin = 7.5:7.5), Cl- uptake increased slightly when an inside-positive membrane potential was applied, but uphill transport was never observed. A pH gradient (pHout:pHin = 5.0:7.5) induced both a 400% increase in the initial Cl- influx rate and a long-lasting (20 to 300 s) overshoot, indicating that a proton gradient can furnish the driving force for uphill Cl- transport. Under pH gradient conditions, initial Cl- entry rates had the following characteristics. (1) They were unaffected by cis-Na+ and/or -K+, indicating the absence of Cl-/K+, Cl-/Na+ or Cl-/K+/Na+ symport activity. (2) Inhibition by 20-100 mM-trans-Na+ and/or -K+ occurred, independent of the existence of an ion gradient. (3) Cl- entry was practically unaffected by short-circuiting the membrane potential with equilibrated potassium and valinomycin. (4) Carbonyl cyanide m-chlorophenylhydrazone was strongly inhibitory and so, to a lesser extent, was 4-acetamido-4'-isothiocyanostilbene-2,2'-disulphonic acid [(SITS)], independent of the sign and size of the membrane potential. (5) Cl- entry was negligibly increased (less than 30%) by either trans-Cl- or -HCO3-, indicating the absence of an obligatory Cl-/anion antiport activity. In contrast, the height of the overshoot at 60 s was increased by trans-Cl-, indicating time-dependent inhibition of 36Cl efflux. That competitive inhibition of 36Cl fluxes by anions is involved here is supported by initial influx rate experiments demonstrating: (1) the saturability of Cl- influx, which was found to exhibit Michaelis-Menten kinetics; and (2) competitive inhibition of influx by cis-Cl- and -Br-. Quantitatively, the conclusion is warranted that over 85% of the total initial Cl- uptake energized by a pH gradient involves an electroneutral Cl-/H+ symporter or its physicochemical equivalent, a Cl-/OH- antiporter, exhibiting little Cl- uniport and either Cl-/Cl- or Cl-/HCO3- antiport activities.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:2597129

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion.

PubMed

Shipley, Heather J; Engates, Karen E; Grover, Valerie A

2013-03-01

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.

Removal of heavy metal species from industrial sludge with the aid of biodegradable iminodisuccinic acid as the chelating ligand.

PubMed

Wu, Qing; Duan, Gaoqi; Cui, Yanrui; Sun, Jianhui

2015-01-01

High level of heavy metals in industrial sludge was the obstacle of sludge disposal and resource recycling. In this study, iminodisuccinic acid (IDS), a biodegradable chelating ligand, was used to remove heavy metals from industrial sludge generated from battery industry. The extraction of cadmium, copper, nickel, and zinc from battery sludge with aqueous solution of IDS was studied under various conditions. It was found that removal efficiency greatly depends on pH, chelating agent's concentration, as well as species distribution of metals. The results showed that mildly acidic and neutral systems were not beneficial to remove cadmium. About 68 % of cadmium in the sample was extracted at the molar ratio of IDS to heavy metals 7:1 without pH adjustment (pH 11.5). Copper of 91.3 % and nickel of 90.7 % could be removed by IDS (molar ratio, IDS: metals = 1:1) with 1.2 % phosphoric acid effectively. Removal efficiency of zinc was very low throughout the experiment. Based on the experimental results, IDS could be a potentially useful chelant for heavy metal removal from battery industry sludge.

Impact of AMD on water quality in critical watershed in the Hudson River drainage basin: Phillips Mine, Hudson Highlands, New York

USGS Publications Warehouse

Gilchrist, S.; Gates, A.; Szabo, Z.; Lamothe, P.J.

2009-01-01

A sulfur and trace element enriched U-Th-laced tailings pile at the abandoned Phillips Mine in Garrison, New York, releases acid mine drainage (AMD, generally pH < 3, minimum pH 1.78) into the first-order Copper Mine Brook (CMB) that drains into the Hudson River. The pyrrhotite-rich Phillips Mine is located in the Highlands region, a critical water source for the New York metro area. A conceptual model for derivation/dissolution, sequestration, transport and dilution of contaminants is proposed. The acidic water interacts with the tailings, leaching and dissolving the trace metals. AMD evaporation during dry periods concentrates solid phase trace metals and sulfate, forming melanterite (FeSO4.7H2O) on sulfide-rich tailings surfaces. Wet periods dissolve these concentrates/precipitates, releasing stored acidity and trace metals into the CMB. Sediments along CMB are enriched in iron hydroxides which act as sinks for metals, indicating progressive sequestration that correlates with dilution and sharp rise in pH when mine water mixes with tributaries. Seasonal variations in metal concentrations were partly attributable to dissolution of the efflorescent salts with their sorbed metals and additional metals from surging acidic seepage induced by precipitation.

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine.

PubMed

Akob, Denise M; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-08-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Identification of Mn(II)-Oxidizing Bacteria from a Low-pH Contaminated Former Uranium Mine

PubMed Central

Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments. PMID:24928873

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine

USGS Publications Warehouse

Akob, Denise M.; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments.

Remediation of AMD using industrial waste adsorbents

NASA Astrophysics Data System (ADS)

Mohammed, Nuur Hani Bte; Yaacob, Wan Zuhairi Wan

2016-11-01

The study investigates the characteristic of industrial waste as adsorbents and its potential as heavy metals absorbents in AMD samples. The AMD sample was collected from active mine pond and the pH was measured in situ. The metal contents were analyzed by ICP-MS. The AMD water was very acidic (pH< 3.5), and the average heavy metals content in AMD were high especially in Fe (822.029 mg/l). Fly ash was found to be the most effective absorbent material containing high percentage of CaO (57.24%) and SiO2 (13.88%), followed by ladle furnace slag containing of high amount of CaO (51.52%) and Al2O3 (21.23%), while biomass ash consists of SiO2 (43.07%) and CaO (12.97%). Tank analysis display a huge changes due to pH value change from acidity to nearly neutral phases. After 50 days, fly ash remediation successfully increase the AMD pH values from pH 2.57-7.09, while slag change from acidity to nearly alkaline phase from pH 2.60-7.3 and biomass has change to pH 2.54-6.8. Fly ash has successfully remove Fe, Mn, Cu, and Ni. Meanwhile, slag sample displays as an effective adsorbent to adsorb more Pb and Cd in acid mine drainage.

Hydrometallurgical Treatment for Mixed Waste Battery Material

NASA Astrophysics Data System (ADS)

Ma, L. W.; Xi, X. L.; Zhang, Z. Z.; Huang, Z. Q.; Chen, J. P.

2017-02-01

Hydrometallurgical experiments are generally required to assess the appropriate treatment process before the establishment of the industrial recovery process for waste battery materials. The effects of acid systems and oxidants in metal leaching were studied. The comprehensive leaching effects of the citric acid were superior to the sulfuric acid. The potassium permanganate inhibits the dissolution of metals. Thermodynamic calculations showed that metals precipitate more easily in sulfuric acid system than in citric acid system. The Fe precipitation efficiency in sulfuric acid system was 90% at pH 3.5, but with considerable losses of Co (30%) and Ni (40%). The proper pH and organic/aqueous (O/A) ratio for Fe and Zn removal with Di-(2-ethylhexyl) phosphoric acid extraction were 2 and 0.5, respectively; while for the removal of Cu and Mn, the best pH and O/A ratio were 3 and 0.75, respectively. Crude manganese carbonate and a cobalt-nickel enriched liquid were obtained by selective precipitation in raffinate using an ammonium bicarbonate solution. In citric acid systems, the precipitation efficiency of Co, Ni, Mn, Fe, Cu and Zn were less than 20% at pH 7. The proper pH and O/A ratio for the separation of the metals in two groups (Ni/Co/Cu and Mn/Fe/Zn) were 1.5 and 2. The cobalt-nickel-copper enriched liquid was finally obtained.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

pH profile of the adsorption of nucleotides onto montmorillonite. I - Selected homoionic clays

NASA Technical Reports Server (NTRS)

Lawless, J. G.; Church, F. M.; Mazzurco, J.; Banin, A.; Huff, R.; Kao, J.; Cook, A.; Lowe, T.; Orenberg, J. B.; Edelson, E.

1985-01-01

The effect of pH and adsorbed ions on the adsorption of purine and pyrimidine nucleotides on montmorillonite clay was studied experimentally. The specific nucleotides examined were: 5 prime-AMP; 3-prime AMP; and 5 prime-CMP. The pH of the clay samples was adjusted to various levels in the 2-12 pH range using microliter volumes of concentrated acid (1N HCl) and base (1NHNaOH). It was found that preferential adsorption among nulceotides was dependent on the pH level and on the characteristics of the substituted metal cation and anion exchange mechanisms. Below pH 4, adsorption was attributed to cation and anion exchange mechanisms. Above pH 4, however, adsorption was attributed to the complexation mechanisms occurring between the metal cations in the clay exchange site and in the biomolecule. The possible role of homoionic clays in the concentration mechanisms of biomonomers in the prebiotic environment is discussed.

Leaching Behavior of Selected Trace and Toxic Metals in Coal Fly Ash Samples Collected from Two Thermal Power Plants, India.

PubMed

Sandeep, P; Sahu, S K; Kothai, P; Pandit, G G

2016-09-01

Studies on leaching behavior of metals associated with coal fly ash (FA) are of great concern because of possible contamination of the aquatic environment. In the present study, leaching behavior of metals (As, Se, Cr, Pb, V, Zn, etc.) in two different FA samples (FA1 and FA2) was investigated at various pH (2-12), temperatures of leachate solution and using TCLP. At pH 2, the highest leaching was observed for Fe (21.6 and 32.8 µg/g), whereas at pH 12, Arsenic was found to have the highest leaching (1.5 and 2.4 µg/g) in FA1 and FA2. Leachate solution temperature showed a positive effect on the metal's leachability. In TCLP, most of the metal's leachability was observed to be higher than that of batch leaching tests. The present study suggests that, leaching of As and Se from FA samples can moderately affect ground/surface water quality at the study locations.

Metal concentrations in aquatic macrophytes as influenced by soil and acidification

USGS Publications Warehouse

Sparling, D.W.; Lowe, T.P.

1998-01-01

Bioavailability of metals to aquatic plants is dependent on many factors including ambient metal concentration, pH of soil or water, concentration of ligands, competition with other metals for binding sites, and mode of exposure. Plants may be exposed to metals through water, air, or soil, depending on growth form. This paper examines the influence of soil type under two regimens of water acidification on metal uptake by four species of aquatic macrophytes: smartweed (Polygonum sagittatum), burreed (Sparganium americanum), pondweed (Potamogeton diversifolius), and bladderwort (Utricularia vulgaris) in constructed, experimentally acidified wetlands. Soil types consisted of a comparatively high-metal clay or a lower-metal sandy loam. Each pond was either acidified to pH ca. 4.85.3 or allowed to remain circumneutral. Metal concentrations tended to be higher in the submerged bladderwort and pondweed than in the emergent burreed and smartweed. Soils were important to plant metal concentrations in all species, but especially in the emergents. Acidification influenced plant concentrations of some metals and was especially important in the submerged pondweed. Bioaccumulation of metals occurred for Mn, B, Sr, Ba, and Zn, compared to soil concentrations.

Metal resistance in acidophilic microorganisms and its significance for biotechnologies.

PubMed

Dopson, Mark; Holmes, David S

2014-10-01

Extremely acidophilic microorganisms have an optimal pH of <3 and are found in all three domains of life. As metals are more soluble at acid pH, acidophiles are often challenged by very high metal concentrations. Acidophiles are metal-tolerant by both intrinsic, passive mechanisms as well as active systems. Passive mechanisms include an internal positive membrane potential that creates a chemiosmotic gradient against which metal cations must move, as well as the formation of metal sulfate complexes reducing the concentration of the free metal ion. Active systems include efflux proteins that pump metals out of the cytoplasm and conversion of the metal to a less toxic form. Acidophiles are exploited in a number of biotechnologies including biomining for sulfide mineral dissolution, biosulfidogenesis to produce sulfide that can selectively precipitate metals from process streams, treatment of acid mine drainage, and bioremediation of acidic metal-contaminated milieux. This review describes how acidophilic microorganisms tolerate extremely high metal concentrations in biotechnological processes and identifies areas of future work that hold promise for improving the efficiency of these applications.

Perspectives regarding the use of metallurgical slags as secondary metal resources - A review of bioleaching approaches.

PubMed

Potysz, Anna; van Hullebusch, Eric D; Kierczak, Jakub

2018-05-05

Smelting activity by its very nature produces large amounts of metal-bearing waste, often called metallurgical slag(s). In the past, industry used to dispose of these waste products at dumping sites without the appropriate environmental oversight. Once there, ongoing biogeochemical processes affect the stability of the slags and cause the release of metallic contaminants. Rather than viewing metallurgical slags as waste, however, such deposits should be viewed as secondary metal resources. Metal bioleaching is a "green" treatment route for metallurgical slags, currently being studied under laboratory conditions. Metal-laden leachates obtained at the bioleaching stage have to be subjected to further recovery operations in order to obtain metal(s) of interest to achieve the highest levels of purity possible. This perspective paper considers the feasibility of the reuse of base-metal slags as secondary metal resources. Special focus is given to current laboratory bioleaching approaches and associated processing obstacles. Further directions of research for development of more efficient methods for waste slag treatment are also highlighted. The optimized procedure for slag treatment is defined as the result of this review and should include following steps: i) slag characterization (chemical and phase composition and buffering capacity) following the choice of initial pH, ii) the choice of particle size, iii) the choice of the liquid-to-solid ratio, iv) the choice of microorganisms, v) the choice of optimal nutrient supply (growth medium composition). An optimal combination of all these parameters will lead to efficient extraction and generation of metal-free solid residue. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

In vitro removal of toxic heavy metals by poly(γ-glutamic acid)-coated superparamagnetic nanoparticles

PubMed Central

Inbaraj, Baskaran Stephen; Chen, Bing-Huei

2012-01-01

Background: Chelation therapy involving organic chelators for treatment of heavy metal intoxication can cause cardiac arrest, kidney overload, mineral deficiency, and anemia. Methods: In this study, superparamagnetic iron oxide nanoparticles (SPIONs) modified with an edible biopolymer poly(γ-glutamic acid) (PGA) were synthesized by coprecipitation method, characterized and evaluated for their removal efficiency of heavy metals from a metal solution, and simulated gastrointestinal fluid (SGIF). Results: Instrumental characterization of bare- and PGA-SPIONs revealed 7% coating of PGA on SPIONs with a spherical shape and an iron oxide spinel structure belonging to magnetite. The particle sizes as determined from transmission electron microscopy images were 8.5 and 11.7 nm for bare- and PGA-SPIONs, respectively, while the magnetization values were 70.3 and 61.5 emu/g. Upon coating with PGA, the zeta potentials were shifted from positive to negative at most of the environmental pH (3–8) and biological pH (1–8), implying good dispersion in aqueous suspension and favorable conditions for heavy metal removal. Batch studies showed rapid removal of lead and cadmium with the kinetic rates estimated by pseudo-second-order model being 0.212 and 0.424 g/mg·min, respectively. A maximum removal occurred in the pH range 4–8 in deionized water and 5–8 in SGIF corresponding to most gastrointestinal pH except for the stomach. Addition of different ionic strengths (0.001–1 M sodium acetate) and essential metals (Cu, Fe, Zn, Mg, Ca, and K) did not show any marked influence on lead removal by PGA-SPIONs, but significantly reduced the binding of cadmium. Compared to deionized water, the lead removal from SGIF was high at all pH with the Langmuir monolayer removal capacity being 98.70 mg/g for the former and 147.71 mg/g for the latter. However, a lower cadmium removal capacity was shown for SGIF (23.15 mg/g) than for deionized water (31.13 mg/g). Conclusion: These results suggest that PGA-SPIONs could be used as a metal chelator for clinical treatment of metal poisoning. PMID:22927758

Surprising abundance of Gallionella-related iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations

USGS Publications Warehouse

Fabisch, Maria; Beulig, Felix; Akob, Denise M.; Küsel, Kirsten

2013-01-01

We identified and quantified abundant iron-oxidizing bacteria (FeOB) at three iron-rich, metal-contaminated creek sites with increasing sediment pH from extremely acidic (R1, pH 2.7), to moderately acidic (R2, pH 4.4), to slightly acidic (R3, pH 6.3) in a former uranium-mining district. The geochemical parameters showed little variations over the 1.5 year study period. The highest metal concentrations found in creek sediments always coincided with the lowest metal concentrations in creek water at the slightly acidic site R3. Sequential extractions of R3 sediment revealed large portions of heavy metals (Ni, Cu, Zn, Pb, U) bound to the iron oxide fraction. Light microscopy of glass slides exposed in creeks detected twisted stalks characteristic of microaerobic FeOB of the family Gallionellaceae at R3 but also at the acidic site R2. Sequences related to FeOB such as Gallionella ferruginea, Sideroxydans sp. CL21, Ferritrophicum radicicola, and Acidovorax sp. BrG1 were identified in the sediments. The highest fraction of clone sequences similar to the acidophilic “Ferrovum myxofaciens” was detected in R1. Quantitative PCR using primer sets specific for Gallionella spp., Sideroxydans spp., and “Ferrovum myxofaciens” revealed that ~72% (R2 sediment) and 37% (R3 sediment) of total bacterial 16S rRNA gene copies could be assigned to groups of FeOB with dominance of microaerobic Gallionella spp. at both sites. Gallionella spp. had similar and very high absolute and relative gene copy numbers in both sediment communities. Thus, Gallionella-like organisms appear to exhibit a greater acid and metal tolerance than shown before. Microaerobic FeOB from R3 creek sediment enriched in newly developed metal gradient tubes tolerated metal concentrations of 35 mM Co, 24 mM Ni, and 1.3 mM Cd, higher than those in sediments. Our results will extend the limited knowledge of FeOB at contaminated, moderately to slightly acidic environments.

Fractionation and leachability of heavy metals from aged and recent Zn metallurgical leach residues from the Três Marias zinc plant (Minas Gerais, Brazil).

PubMed

Sethurajan, Manivannan; Huguenot, David; Lens, Piet N L; Horn, Heinrich A; Figueiredo, Luiz H A; van Hullebusch, Eric D

2016-04-01

Various mineral processing operations to produce pure metals from mineral ores generate sludges, residues, and other unwanted by-products/wastes. As a general practice, these wastes are either stored in a reservoir or disposed in the surrounding of mining/smelting areas, which might cause adverse environmental impacts. Therefore, it is important to understand the various characteristics like heavy metal leaching features and potential toxicity of these metallurgical wastes. In this study, zinc plant leach residues (ZLRs) were collected from a currently operating Zn metallurgical industry located in Minas Gerais (Brazil) and investigated for their potential toxicity, fractionation, and leachability. Three different ZLR samples (ZLR1, ZLR2, and ZLR3) were collected, based on their age of production and deposition. They mainly consisted of Fe (6-11.5 %), Zn (2.5 to 5.0 %), and Pb (1.5 to 2.5 %) and minor concentrations of Al, Cd, Cu, and Mn, depending on the sample age. Toxicity Characteristic Leaching Procedure (TCLP) results revealed that these wastes are hazardous for the environment. Accelerated Community Bureau of Reference (BCR) sequential extraction clearly showed that potentially toxic heavy metals such as Cd, Cu, Pb, and Zn can be released into the environment in high quantities under mild acidic conditions. The results of the liquid-solid partitioning as a function of pH showed that pH plays an important role in the leachability of metals from these residues. At low pH (pH 2.5), high concentrations of metals can be leached: 67, 25, and 7 % of Zn can be leached from leach residues ZLR1, ZLR2, and ZLR3, respectively. The release of metals decreased with increasing pH. Geochemical modeling of the pH-dependent leaching was also performed to determine which geochemical process controls the leachability/solubility of the heavy metals. This study showed that the studied ZLRs contain significant concentrations of non-residual extractable fractions of Zn and can be seen as a potential secondary resource for Zn.

Use of a chemical equilibrium model to describe surface properties and uptake of cadmium, strontium, and lead by Chlorella (UTEX 252)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hassett, J.M.

1988-01-01

Metal-aquatic biota interactions are important in both natural and engineered systems. In this study, the uptake of cadmium, strontium and lead by the unicellular green alga Chlorella (UTEX 252) was investigated. Variables included metal concentration, pH, and ionic strength. Data gathered included dry weights (mg/l), cell counts (cells/ml), electrophoretic mobilities (EPMs, {mu}m/sec/V/cm) of metal-free and metal-exposed cells, and metal uptake - difference in concentration in filtrate of cell-metal and cell-free metal solutions. Derived data included cell volumes and surface area, uptake on a {mu}M/m{sup 2} basis, {zeta}-potentials, diffuse layer potentials and charge densities. Typical uptake values were 1.1, 5.2, andmore » 6 {mu}M/m{sup 2} for Cd, Pb, and Sr, respectively, from solutions of pH 6, ionic strength 0.02M, and metal concentration 10{sup {minus}4} M. Cell EPMs were insensitive to metal; under certain conditions, however, (pM > 4, pH > 8), cadmium exposed cells exhibited a reversal in surface charge from negative to positive. The chemical equilibrium model MINEQL1 + STANFORD was used to model algal surface properties and metal uptake. Input data included site pK, density, and {Delta}pK, estimated from EPM-pH data. The model described surface properties of Chlorella (UTEX 252) as judged by a close fit of {zeta}-potentials and model-derived diffuse layer potentials. Metal uptake was modelled by adjusting site density and/or metal-surface site equilibrium constants. Attempts to model surface properties and metal uptake simultaneously were not successful.« less

Changes in heavy metal bioavailability and speciation from a Pb-Zn mining soil amended with biochars from co-pyrolysis of rice straw and swine manure.

PubMed

Meng, Jun; Tao, Mengming; Wang, Lili; Liu, Xingmei; Xu, Jianming

2018-08-15

Biochar has been utilized as a good amendment to immobilize heavy metals in contaminated soils. However, the effectiveness of biochar in metal immobilization depends on biochar properties and metal species. In this study, the biochars produced from co-pyrolysis of rice straw with swine manure at 400°C were investigated to evaluate their effects on bioavailability and chemical speciation of four heavy metals (Cd, Cu, Pb and Zn) in a Pb-Zn contaminated soil through incubation experiment. Results showed that co-pyrolysis process significantly change the yield, ash content, pH, and electrical conductivity (EC) of the blended biochars compared with the single straw/manure biochar. The addition of these biochars significantly increased the soil pH, EC, and dissolved organic carbon (DOC) concentrations. The addition of biochars at a rate of 3% significantly reduced the CaCl 2 -extractable metal concentrations in the order of Pb>Cu>Zn>Cd. The exchangeable heavy metals decreased in all the biochar-amended soils whereas the carbonate-bound metal speciation increased. The increase in soil pH and the decrease in the CaCl 2 extractable metals indicated that these amendments can directly transform the highly availability metal speciation to the stable speciation in soils. In conclusion, biochar derived from co-pyrolysis of rice straw with swine manure at a mass ratio of 3:1 could most effectively immobilize the heavy metals in the soil. Copyright © 2018 Elsevier B.V. All rights reserved.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, Wen Y.

1984-01-01

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Comparison of heavy metals and uranium removal using adsorbent in soil

NASA Astrophysics Data System (ADS)

Choi, Jaeyoung; Yun, Hunsik

2017-04-01

This study investigates heavy metals (As, Ni, Zn, Cd, and Pb) and uranium removal onto geomaterials (limestone, black shale, and concrete) and biosorbents (Pseudomonas putida and starfish) from waste in soil. Geomaterials or biosorbents with a high capacity for heavy metals and uranium can be obtained and employed of with little cost. For investigating the neutralization capacity, the change in pH, Eh, and EC as a function of time was quantified. The adsorption of heavy metals and uranium by the samples was influenced by pH, and increased with increasing heavy metals and uranium concentrations. Dead cells adsorbed the largest quantity of all heavy metals than lother sorbents. The adsorption capacity followed the order: U(VI) > Pb > Cd > Ni. The results also suggest that bacterial membrane cells can be used successfully in the treatment of high strength metal-contaminated soil.

Ion exchange selectivity for cross-linked polyacrylic acid

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.

1983-01-01

The ion separation factors for 21 common metal ions with cross-linked polyacrylic acid were determined as a function of pH and the percent of the cross-linked polyacrylic acid neutralized. The calcium ion was used as a reference. At a pH of 5 the decreasing order of affinity of the ions for the cross-linked polyacrylic acid was found to be: Hg++, Fe+++, Pb++, Cr+++, Cu++, Cd++, Al+++, Ag+, Zn++, Ni++, Mn++, Co++, Ca++, Sr++, Ba++, Mg++, K+, Rb+, Cs+, Na+, and Li+. Members of a chemical family exhibited similar selectivities. The Hg++ ion appeared to be about a million times more strongly bound than the alkali metal ions. The relative binding of most of the metal ions varied with pH; the very tightly and very weakly bound ions showed the largest variations with pH. The calcium ion-hydrogen ion equilibrium was perturbed very little by the presence of the other ions. The separation factors and selectivity coefficients are discussed in terms of equilibrium and thermodynamic significance.

Tris(phosphinoamide)-supported uranium-cobalt heterobimetallic complexes featuring Co → U dative interactions.

PubMed

Napoline, J Wesley; Kraft, Steven J; Matson, Ellen M; Fanwick, Phillip E; Bart, Suzanne C; Thomas, Christine M

2013-10-21

A series of tris- and tetrakis(phosphinoamide) U/Co complexes has been synthesized. The uranium precursors, (η(2)-Ph2PN(i)Pr)4U (1), (η(2)-(i)Pr2PNMes)4U (2), (η(2)-Ph2PN(i)Pr)3UCl (3), and (η(2)-(i)Pr2PNMes)3UI (4), were easily accessed via addition of the appropriate stoichiometric equivalents of [Ph2PN(i)Pr]K or [(i)Pr2PNMes]K to UCl4 or UI4(dioxane)2. Although the phosphinoamide ligands in 1 and 4 have been shown to coordinate to U in an η(2)-fashion in the solid state, the phosphines are sufficiently labile in solution to coordinate cobalt upon addition of CoI2, generating the heterobimetallic Co/U complexes ICo(Ph2PN(i)Pr)3U[η(2)-Ph2PN(i)Pr] (5), ICo((i)Pr2PNMes)3U[η(2)-((i)Pr2PNMes)] (6), ICo(Ph2PN(i)Pr)3UI (7), and ICo((i)Pr2PNMes)3UI (8). Structural characterization of complexes 5 and 7 reveals reasonably short Co-U interatomic distances, with 7 exhibiting the shortest transition metal-uranium distance ever reported (2.874(3) Å). Complexes 7 and 8 were studied by cyclic voltammetry to examine the influence of the metal-metal interaction on the redox properties compared with both monometallic Co and heterobimetallic Co/Zr complexes. Theoretical studies are used to further elucidate the nature of the transition metal-actinide interaction.

Characteristics and metal leachability of incinerated sewage sludge ash and air pollution control residues from Hong Kong evaluated by different methods.

PubMed

Li, Jiang-Shan; Xue, Qiang; Fang, Le; Poon, Chi Sun

2017-06-01

The improper disposal of incinerated sewage sludge ash (ISSA) and air pollution control residues (APCR) from sewage sludge incinerators has become an environmental concern. The physicochemical, morphological and mineralogical characteristics of ISSA and APCR from Hong Kong, and the leachability and risk of heavy metals, are presented in this paper. The results showed that a low hydraulic and pozzolanic potential was associated with the ISSA and APCR due to the presence of low contents of SiO 2 , Al 2 O 3 and CaO and high contents of P, S and Cl (especially for APCR). Although high concentrations of Zn and Cu (especially for ISSA) followed by Ni, Pb and As, Se were detected, a low leaching rate of these metals (especially at neutral and alkaline pH) rendered them classifiable as non-hazardous according to the U.S. EPA and Chinese national regulatory limits. The leached metals concentrations from ISSA and APCR were mainly pH dependent, and metals solubilization occurred mainly at low pH. Different leaching tests should be adopted based on the simulated different environmental conditions and exposure scenarios for assessing the leachability as contrasting results could be obtained due to the differences in complexing abilities and final pH of the leaching solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Scaling theory in a model of corrosion and passivation.

PubMed

Aarão Reis, F D A; Stafiej, Janusz; Badiali, J-P

2006-09-07

We study a model for corrosion and passivation of a metallic surface after small damage of its protective layer using scaling arguments and simulation. We focus on the transition between an initial regime of slow corrosion rate (pit nucleation) to a regime of rapid corrosion (propagation of the pit), which takes place at the so-called incubation time. The model is defined in a lattice in which the states of the sites represent the possible states of the metal (bulk, reactive, and passive) and the solution (neutral, acidic, or basic). Simple probabilistic rules describe passivation of the metal surface, dissolution of the passive layer, which is enhanced in acidic media, and spatially separated electrochemical reactions, which may create pH inhomogeneities in the solution. On the basis of a suitable matching of characteristic times of creation and annihilation of pH inhomogeneities in the solution, our scaling theory estimates the average radius of the dissolved region at the incubation time as a function of the model parameters. Among the main consequences, that radius decreases with the rate of spatially separated reactions and the rate of dissolution in acidic media, and it increases with the diffusion coefficient of H(+) and OH(-) ions in solution. The average incubation time can be written as the sum of a series of characteristic times for the slow dissolution in neutral media, until significant pH inhomogeneities are observed in the dissolved cavity. Despite having a more complex dependence on the model parameters, it is shown that the average incubation time linearly increases with the rate of dissolution in neutral media, under the reasonable assumption that this is the slowest rate of the process. Our theoretical predictions are expected to apply in realistic ranges of values of the model parameters. They are confirmed by numerical simulation in two-dimensional lattices, and the expected extension of the theory to three dimensions is discussed.

Attenuation of landfill leachate by UK Triassic sandstone aquifer materials. 1. Fate of inorganic pollutants in laboratory columns

NASA Astrophysics Data System (ADS)

Thornton, Steven F.; Tellam, John H.; Lerner, David N.

2000-05-01

The attenuation of inorganic contaminants in acetogenic and methanogenic landfill leachate by calcareous and carbonate-deficient, oxide-rich Triassic sandstone aquifer materials from the English Midlands was examined in laboratory columns. Aqueous equilibrium speciation modelling, simple transport modelling and chemical mass balance approaches are used to evaluate the key processes and aquifer geochemical properties controlling contaminant fate. The results indicate that leachate-rock interactions are dominated by ion-exchange processes, acid-base and redox reactions and sorption/precipitation of metal species. Leachate NH 4 is attenuated by cation exchange with the aquifer sediments; however, NH 4 migration could be described with a simple model using retardation factors. Organic acids in the acetogenic leachate buffered the system pH at low levels during flushing of the calcareous aquifer material. In contrast, equilibrium with Al oxyhydroxide phases initially buffered pH (˜4.5) during flushing of the carbonate-deficient sandstone with methanogenic leachate. This led to the mobilisation of sorbed and oxide-bound heavy metals from the aquifer sediment which migrated as a concentrated pulse at the leachate front. Abiotic reductive dissolution of Mn oxyhydroxides on each aquifer material by leachate Fe 2+ maintains high concentrations of dissolved Mn and buffers the leachate inorganic redox system. This feature is analogous to the Mn-reducing zones found in leachate plumes and in the experiments provides a sink for the leachate Fe load and other heavy metals. The availability of reactive solid phase Mn oxyhydroxides limits the duration of redox buffering and Fe attenuation by these aquifer sediments. Aquifer pH and redox buffering capacity exert a fundamental influence on leachate inorganic contaminant fate in these systems. The implications for the assessment of aquifer vulnerability at landfills are discussed and simple measurements of aquifer properties which may improve the prediction of contaminant attenuation are outlined.

Heavy Metals Biosorption from Aqueous Solution by Endophytic Drechslera hawaiiensis of Morus alba L. Derived from Heavy Metals Habitats

PubMed Central

Hassanein, Naziha M.; Abd El-Hay Ibrahim, Hussein; Abd El-Baky, Doaa H.

2017-01-01

The ability of dead cells of endophytic Drechslera hawaiiensis of Morus alba L. grown in heavy metals habitats for bioremoval of cadmium (Cd2+), copper (Cu2+), and lead (Pb2+) in aqueous solution was evaluated under different conditions. Whereas the highest extent of Cd2+ and Cu2+ removal and uptake occurred at pH 8 as well as Pb2+ occurred at neutral pH (6–7) after equilibrium time 10 min. Initial concentration 30 mg/L of Cd2+ for 10 min contact time and 50 to 90 mg/L of Pb2+ and Cu2+ supported the highest biosorption after optimal contact time of 30 min achieved with biomass dose equal to 5 mg of dried died biomass of D. hawaiiensis. The maximum removal of Cd2+, Cu2+, and Pb2+ equal to 100%, 100%, and 99.6% with uptake capacity estimated to be 0.28, 2.33, and 9.63 mg/g from real industrial wastewater, respectively were achieved within 3 hr contact time at pH 7.0, 7.0, and 6.0, respectively by using the dead biomass of D. hawaiiensis compared to 94.7%, 98%, and 99.26% removal with uptake equal to 0.264, 2.3, and 9.58 mg/g of Cd2+, Cu2+, and Pb2+, respectively with the living cells of the strain under the same conditions. The biosorbent was analyzed by Fourier Transformer Infrared Spectroscopy (FT-IR) analysis to identify the various functional groups contributing in the sorption process. From FT-IR spectra analysis, hydroxyl and amides were the major functional groups contributed in biosorption process. It was concluded that endophytic D. hawaiiensis biomass can be used potentially as biosorbent for removing Cd2+, Cu2+, and Pb2+ in aqueous solutions. PMID:28781539

INFLUENCE OF PH AND REDOX CONDITIONS ON COPPER LEACHING

EPA Science Inventory

Leaching behavior of metals from a mineral processing waste at varying pH and redox conditions was studies. Effect of combinations of pH and Eh on leaching of copper is described. Leaching of copper was found to be dependent on both pH and Eh. Higher concentrations of Cu were ...

Recovery of soil nitrification after long-term zinc exposure and its co-tolerance to Cu in different soils.

PubMed

Liu, Aiju; Fang, Dianmei; Wang, Chao; Li, Menghong; Young, Robert B

2015-01-01

Soils sampled from different locations of China were used to manipulate soil microbial diversity and to assess the effect of the diversity of the soil nitrifying community on the recovery of the soil nitrification to metal stress (zinc). Ten treatments were either or not amended with ZnCl2. Subsequently, a spike-on-spike assay was set up to test for the tolerance of soil nitrification to zinc (Zn) and copper (Cu). Initially, Zn amendment completely inhibited nitrification. After a year of Zn exposure, recovery of the potential nitrification rate in Zn-amended soils ranged from 28 to 126% of the potential nitrification rate in the corresponding Zn-nonamended soils. This recovery was strongly related to the potential nitrification rate before Zn amendment and soil pH. Increased Zn tolerance of the soil nitrification was consistently observed in response to corresponding soil contamination. Co-tolerance to Cu was obtained in all 1,000-mg kg(-1) Zn-amended soils. This tolerance was also strongly related to the potential nitrification rate before Zn amendment and soil pH. Our data indicate that inherently microbial activity can be a significant factor for the recovery of soil functioning derived from metal contamination.

Lead-induced stress corrosion cracking of Alloy 600 and 690 in high temperature water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakai, T.; Senjuh, T.; Aoki, K.

1992-12-31

Lead is one of the potential contributing impurities to the degradation of PWR steam generator tubing. Recent laboratory testing has shown that lead is a corrosive material for Alloy 600 steam generator tubing. However, it is still unknown how lead influences the corrosion of steam generator tubing, including the effect of lead concentration, solution pH, stress level and material characteristics. In this study, two kinds of experiments were performed. One was to investigate the thin film characteristic and selectively dissolved base metal elements of Alloy 600MA in high temperature solutions of different lead concentrations and pH. The other investigated themore » dependency of degradation of Alloy 600MA and Alloy 690TT on lead concentration and stress level in mild acidic environment, at 340{degrees}C for 2500 hrs. It was firstly demonstrated that lead-enhanced selective dissolution of nickel from alloy base metal, as a result of electrochemical reaction between lead and nickel, might cause the initiation and propagation of corrosion. Secondly, we showed that Alloy 690TT, generally very corrosion resistant material, also suffered from Pb-induced corrosion. The difference of the lead-induced stress corrosion morphology of Alloy 600MA and Alloy 690TT was also clarified.« less

On-column nitrosation of amines observed in liquid chromatography impurity separations employing ammonium hydroxide and acetonitrile as mobile phase.

PubMed

Myers, David P; Hetrick, Evan M; Liang, Zhongming; Hadden, Chad E; Bandy, Steven; Kemp, Craig A; Harris, Thomas M; Baertschi, Steven W

2013-12-06

The availability of high performance liquid chromatography (HPLC) columns capable of operation at pH values up to 12 has allowed a greater selectivity space to be explored for method development in pharmaceutical analysis. Ammonium hydroxide is of particular value in the mobile phase because it is compatible with direct interfacing to electrospray mass spectrometers. This paper reports an unexpected N-nitrosation reaction that occurs with analytes containing primary and secondary amines when ammonium hydroxide is used to achieve the high pH and acetonitrile is used as the organic modifier. The nitrosation reaction has generality. It has been observed on multiple columns from different vendors and with multiple amine-containing analytes. Ammonia was established to be the source of the nitroso nitrogen. The stainless steel column frit and metal ablated from the frit have been shown to be the sites of the reactions. The process is initiated by removal of the chromium oxide protective film from the stainless steel by acetonitrile. It is hypothesized that the highly active, freshly exposed metals catalyze room temperature oxidation of ammonia to NO but that the actual nitrosating agent is likely N(2)O(3). Copyright © 2013 Elsevier B.V. All rights reserved.

Upcycling of polypropylene waste by surface modification using radiation-induced grafting

NASA Astrophysics Data System (ADS)

Hassan, Muhammad Inaam ul; Taimur, Shaista; Yasin, Tariq

2017-11-01

In this work, upcycling of polypropylene waste into amidoxime functionalized polypropylene adsorbent was studied using radiation-induced grafting technique. Polypropylene waste (PPw) was resulted from accelerated thermal ageing of polypropylene (PP). Bulk grafting of acrylonitrile (AN) onto PPw was achieved by simultaneous radiation grafting method using gamma rays. Degree of grafting of AN on PPw is affected by absorbed dose and dose rate. The acrylonitrile groups of grafted PPw were chemically converted into amidoxime functionality. Both the acrylonitrile-grafted PP waste and its amidoxime product were investigated by FTIR, XRD, SEM-EDX and TGA techniques. The prepared amidoxime adsorbent with amidoxime group density of 8.06 mmol/g was used for removal of copper ions from aqueous solutions. The effects of various physicochemical conditions such as: solution pH, adsorbent content, initial metal ion concentration and time on adsorption were studied to maximize adsorption of metal ion. Pseudo-first-order, pseudo-second-order and intra-particle diffusion models were applied to study the kinetics of adsorption. Maximum Langmuir adsorption capacity of 208.3 mg/g at pH 5.0 with optimum contact time of 120 min was observed. Utilization of PP waste and its comparable adsorption capacity with existing radiation grafted polymer-based adsorbents provide a new, cheap and cost effective system.

Characterization of cadmium biosorption by Exiguobacterium sp. isolated from farmland soil near Cu-Pb-Zn mine.

PubMed

Park, Jin Hee; Chon, Hyo-Taek

2016-06-01

Bacteria have the ability to bind heavy metals on their cell wall. Biosorption is a passive and energy-independent mechanism to adsorb heavy metals. The efficiency of heavy metal biosorption can vary depending on several factors such as the growth phase of bacteria, solution pH, and existence of competitive heavy metals. In this study, Exiguobacterium sp. isolated from farmland soil near a mine site were used, and optimal conditions for Cd biosorption in solution were investigated. As bacterial growth progressed, Cd biosorption increased, which is attributed to changes in the structure and composition of the cell wall during bacterial growth. The biosorption process was rapid and was completed within 30 min. Cadmium biosorption was highest at pH 7 due to the dissociation of hydrogen ions and the increase of negative charges with increasing pH. In the mixed metal solution of Cd, Pb, and Zn, the amount of biosorption was in the order of Pb>Cd>Zn while in a single metal solution, the order was Cd≥Pb>Zn. The maximum adsorption capacity for Cd by the isolated bacteria was 15.6 mg/g biomass, which was calculated from the Langmuir isotherm model. Different adsorption efficiencies under various environmental conditions indicate that, to control metal mobility, the conditions for biosorption should be optimized before applying bacteria. The results showed that the isolated bacteria can be used to immobilize metals in metal-contaminated wastewater.

Leaching and geochemical behavior of fired bricks containing coal wastes.

PubMed

Taha, Yassine; Benzaazoua, Mostafa; Edahbi, Mohamed; Mansori, Mohammed; Hakkou, Rachid

2018-03-01

High amounts of mine wastes are continuously produced by the mining industry all over the world. Recycling possibility of some wastes in fired brick making has been investigated and showed promising results. However, little attention is given to the leaching behavior of mine wastes based fired bricks. The objective of this paper is to evaluate the geochemical behavior of fired bricks containing different types of coal wastes. The leachates were analyzed for their concentration of As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Zn and sulfates using different leaching tests; namely Tank Leaching tests (NEN 7375), Toxicity Characteristic Leaching Procedure (TCLP) and pH dependence test (EPA, 1313). The results showed that the release of constituents of potential interest was highly reduced after thermal treatment and were immobilized within the glassy matrix of the fired bricks. Moreover, it was also highlighted that the final pH of all fired samples changed and stabilized around 8-8.5 when the initial pH of leaching solution was in the range 2.5-11.5. The release of heavy metals and metalloids (As) tended to decrease with the increase of pH from acidic to alkaline solutions while Mo displayed a different trend. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characteristics and adsorption study of the activated carbon derived from municipal sewage sludge.

PubMed

Guo, Tiecheng; Yao, Sicong; Chen, Hengli; Yu, Xin; Wang, Meicheng; Chen, Yao

2017-10-01

Sewage sludge-based activated carbon is proved to be an efficient and low-cost adsorbent in treatment of various industrial wastewaters. The produced carbon had a well-developed pore structure and relatively low Brunauer-Emmett-Teller (BET) surface area. Adsorptive capacity of typical pollutants, i.e. copper Cu(II) and methylene blue (MB) on the carbon was studied. Adsorptions were affected by the initial solution pH, contact time and adsorbent dose. Results showed that adsorption of Cu(II) and MB on the produced carbon could reach equilibrium after 240 min. The average removal rate for Cu(II) on the carbon was high, up to 97% in weak acidic conditions (pH = 4-6) and around 98% for MB in a very wide pH range (pH = 2-12). The adsorption kinetics were well fitted by the pseudo-second order model, and both Langmuir and Freundlich isotherm models could well describe the adsorption process at room temperature. The theoretical maximum adsorption capacities of Cu(II) and MB on sewage sludge-based activated carbon were 114.94 mg/g and 125 mg/g, respectively. Compared with commercial carbon, the sewage sludge-based carbon was more suitable for heavy metal ions' removal than dyes'.

Persulfate activation by subsurface minerals.

PubMed

Ahmad, Mushtaque; Teel, Amy L; Watts, Richard J

2010-06-25

Persulfate dynamics in the presence of subsurface minerals was investigated as a basis for understanding persulfate activation for in situ chemical oxidation (ISCO). The mineral-mediated decomposition of persulfate and generation of oxidants and reductants was investigated with four iron and manganese oxides and two clay minerals at both low pH (<7) and high pH (>12). The manganese oxide birnessite was the most effective initiator of persulfate for degrading the oxidant probe nitrobenzene, indicating that oxidants are generated at both low and high pH regimes. The iron oxide goethite was the most effective mineral for degrading the reductant probe hexachloroethane. A natural soil and two soil fractions were used to confirm persulfate activation by synthetic minerals. The soil and soil fractions did not effectively promote the generation of oxidants or reductants. However, soil organic matter was found to promote reductant generation at high pH. The results of this research demonstrate that synthetic iron and manganese oxides can activate persulfate to generate reductants and oxidants; however, iron and manganese oxides in the natural soil studied do not show the same reactivity, most likely due to the lower masses of the metal oxides in the soil relative to the masses studied in isolated mineral systems. 2010. Published by Elsevier B.V.

Soil solution Zn and pH dynamics in non-rhizosphere soil and in the rhizosphere of Thlaspi caerulescens grown in a Zn/Cd-contaminated soil.

PubMed

Luo, Y M; Christie, P; Baker, A J

2000-07-01

Temporal changes in soil solution properties and metal speciation were studied in non-rhizosphere soil and in the rhizosphere of the hyperaccumulator Thlaspi caerulescens J. & C. Presl (population from Prayon, Belgium) grown in a Zn- and Cd-contaminated soil. This paper focuses on soil solution Zn and pH dynamics during phytoextraction. The concentration of Zn in both non-rhizosphere and rhizosphere soil solutions decreased from 23 mg/l at the beginning to 2 mg/l at the end of the experiment (84 days after transplanting of seedlings), mainly due to chemical sorption. There was no significant difference in overall Zn concentration between the planted and the unplanted soil solutions (P > 0.05). Soil solution pH decreased initially and then increased slightly in both planted and unplanted soil zones. From 60 to 84 days after transplanting, the pH of the rhizosphere soil solution was higher than that of non-rhizosphere soil solution (P<0.05). Zn uptake by the hyperaccumulator plants was 8.8 mg per pot (each containing 1 kg oven-dry soil) on average. The data indicate that the potential of T. caerulescens to remove Zn from contaminated soil may not be related to acidification of the rhizosphere.

Coagulation of bitumen with kaolinite in aqueous solutions containing Ca2+, Mg2+ and Fe3+: effect of citric acid.

PubMed

Gan, Weibing; Liu, Qi

2008-08-01

Heterocoagulation experiments of kaolinite with solvent-diluted-bitumen were carried out to investigate the effect of hydrolyzable metal cations and citric acid on the liberation of bitumen from kaolinite. The adsorption of Ca(2+) and Mg(2+) on kaolinite, and zeta potentials of kaolinite and bitumen droplets in solutions containing 10(-3)mol/L of Ca(2+), Mg(2+) and Fe(3+) with or without citric acid were also measured. It was found that the heterocoagulation of bitumen with kaolinite was enhanced in the presence of the metal cations from pH 7 to pH 10.5, accompanied by a decrease in the magnitude of the zeta potentials and an increase in the adsorption of the metal cations on kaolinite and possibly on bitumen droplets. The addition of 5 x 10(-4)mol/L citric acid reduced the degree of coagulation from 90% to less than 40% in the presence of 10(-3)mol/L Ca(2+) and Mg(2+) cations at pH approximately 10, and at pH approximately 8 for Fe(3+). It was found that hydrolyzable metal cations enhanced bitumen-kaolinite interactions through electrical double layer compression and specific adsorption of the metal hydrolysis species on the surface of kaolinite. The effect of metal cations was removed by citric acid through formation of metal-citrate complexes and/or the adsorption of citrate anions, which restored the zeta potentials of both kaolinite and bitumen. Therefore, electrostatic attraction or repulsion was responsible for the coagulation or dispersion of kaolinite particles from bitumen droplets in the tested system.

Dynamic Effects of Initial pH of Substrate on Biological Growth and Metamorphosis of Black Soldier Fly (Diptera: Stratiomyidae).

PubMed

Ma, Junhua; Lei, Yanyan; Rehman, Kashif Ur; Yu, Ziniu; Zhang, Jibin; Li, Wu; Li, Qing; Tomberlin, Jeffery K; Zheng, Longyu

2018-02-08

Edible insects have become a recognized alternative and sustainable source of high-quality proteins and fats for livestock or human consumption. In the production process of black soldier fly (BSF), (Hermetia illucens L. [Diptera: Stratiomyidae]), initial substrate pH is a critical parameter to ensure the best value of insect biomass, life history traits, and quality bio-fertilizer. This study examined the impact of initial pH values on BSF larvae production, development time, and adult longevity. The BSF were reared on artificial diet with initial pH of 2.0, 4.0, 6.0, 8.0, and 10.0; the control was set at 7.0. Final BSF larval weight was significantly greater in substrates having initial pH 6.0 (0.21 g), control 7.0 (0.20 g), and 10.0 (0.20 g) with no significant difference among them, whereas larval weight reared with initial pH 2.0 and 4.0 were lowest at 0.16 g (-23%). Prepupal weight was greatest when larvae were reared on substrates with initial pH 6.0 (0.18 g), control 7.0 (0.19 g), 8.0 (0.18 g), and 10.0 (0.18 g). In contrast, the prepupal weight of larvae reared on diets with initial pH 2.0 was lowest at 0.15 g (-22%). Larval development time was 21.19 d at pH 8.0, about 3 d (12.5%) shorter than that of those reared on diets with initial pH 6.0, 7.0 control, and 10.0. In all treatments, pH shifted to 5.7 after 3-4 d and 8.5 after 16-17 d except for two groups (2.0 and 4.0) where the pH remained slightly acidic 5.0 and 6.5, respectively. © The Author(s) 2018. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Understanding the mobilisation of metal pollution associated with historical mining in a carboniferous upland catchment.

PubMed

Valencia-Avellan, Magaly; Slack, Rebecca; Stockdale, Anthony; Mortimer, Robert John George

2017-08-16

Point and diffuse pollution from metal mining has led to severe environmental damage worldwide. Mine drainage is a significant problem for riverine ecosystems, it is commonly acidic (AMD), but neutral mine drainage (NMD) can also occur. A representative environment for studying metal pollution from NMD is provided by carboniferous catchments characterised by a circumneutral pH and high concentrations of carbonates, supporting the formation of secondary metal-minerals as potential sinks of metals. The present study focuses on understanding the mobility of metal pollution associated with historical mining in a carboniferous upland catchment. In the uplands of the UK, river water, sediments and spoil wastes were collected over a period of fourteen months, samples were chemically analysed to identify the main metal sources and their relationships with geological and hydrological factors. Correlation tests and principal component analysis suggest that the underlying limestone bedrock controls pH and weathering reactions. Significant metal concentrations from mining activities were measured for zinc (4.3 mg l -1 ), and lead (0.3 mg l -1 ), attributed to processes such as oxidation of mined ores (e.g. sphalerite, galena) or dissolution of precipitated secondary metal-minerals (e.g. cerussite, smithsonite). Zinc and lead mobility indicated strong dependence on biogeochemistry and hydrological conditions (e.g. pH and flow) at specific locations in the catchment. Annual loads of zinc and lead (2.9 and 0.2 tonnes per year) demonstrate a significant source of both metals to downstream river reaches. Metal pollution results in a large area of catchment having a depleted chemical status with likely effects on the aquatic ecology. This study provides an improved understanding of geological and hydrological processes controlling water chemistry, which is critical to assessing metal sources and mobilization, especially in neutral mine drainage areas.

Analysis of Stainless Steel Sandwich Panels with a Metal Foam Core for Lightweight Fan Blade Design

NASA Technical Reports Server (NTRS)

Min, James B.; Ghosn, Louis J.; Lerch, Bradley A.; Raj, Sai V.; Holland, Frederic A., Jr.; Hebsur, Mohan G.

2004-01-01

The quest for cheap, low density and high performance materials in the design of aircraft and rotorcraft engine fan and propeller blades poses immense challenges to the materials and structural design engineers. The present study investigates the use of a sandwich foam fan blade mae up of solid face sheets and a metal foam core. The face sheets and the metal foam core material were an aerospace grade precipitation hardened 17-4 PH stainless steel with high strength and high toughness. The resulting structures possesses a high stiffness while being lighter than a similar solid construction. The material properties of 17-4 PH metal foam are reviewed briefly to describe the characteristics of sandwich structure for a fan blade application. A vibration analysis for natural frequencies and a detailed stress analysis on the 17-4 PH sandwich foam blade design for different combinations of kin thickness and core volume are presented with a comparison to a solid titanium blade.

A long-term static immersion experiment on the leaching behavior of heavy metals from waste printed circuit boards.

PubMed

Zhao, Guo-Hua; Luo, Xing-Zhang; Chen, Gui; Zhao, Yong-Jun

2014-08-01

Printed circuit boards (PCBs) are the main components of electrical and electronic equipment (EEE). Waste PCBs contain several kinds of heavy metals, including Cu, Pb and Zn. We characterize the leaching of heavy metals (Cu, Pb, Zn and Ni) from waste PCBs in a pH range of 3.0 to 5.6 using a novel approach based on batch pH-static leaching experiments in this work. The results indicate that the leaching behavior of Cu, Pb, Zn and Ni is strongly dependent on pH. Leaching behavior also varies with different pH values and leaching times. The maximum concentrations of Cu, Pb, Zn and Ni in leachate from waste PCBs were 335.00, 17.57, 2.40 and 2.33 mg L(-1), respectively. The highest Pb, Ni, and Cu concentrations leached significantly exceeded the European Union waste-acceptance limit values with respect to inert waste landfills. The leaching of metals follows the shrinking core model with surface reaction control.

Estimating the Pollution Risk of Cadmium in Soil Using a Composite Soil Environmental Quality Standard

PubMed Central

Huang, Biao; Zhao, Yongcun

2014-01-01

Estimating standard-exceeding probabilities of toxic metals in soil is crucial for environmental evaluation. Because soil pH and land use types have strong effects on the bioavailability of trace metals in soil, they were taken into account by some environmental protection agencies in making composite soil environmental quality standards (SEQSs) that contain multiple metal thresholds under different pH and land use conditions. This study proposed a method for estimating the standard-exceeding probability map of soil cadmium using a composite SEQS. The spatial variability and uncertainty of soil pH and site-specific land use type were incorporated through simulated realizations by sequential Gaussian simulation. A case study was conducted using a sample data set from a 150 km2 area in Wuhan City and the composite SEQS for cadmium, recently set by the State Environmental Protection Administration of China. The method may be useful for evaluating the pollution risks of trace metals in soil with composite SEQSs. PMID:24672364

Decontamination of unsymmetrical dimethylhydrazine waste water by hydrodynamic cavitation-induced advanced Fenton process.

PubMed

Torabi Angaji, Mahmood; Ghiaee, Reza

2015-03-01

A pilot scale hydrodynamic cavitation (HC) reactor, using iron metal blades, as the heterogeneous catalyst, with no external source of H₂O₂ was developed for catalytic decontamination of unsymmetrical dimethylhydrazine (UDMH) waste water. In situ generation of Fenton reagents suggested an induced advanced Fenton process (IAFP) to explain the enhancing effect of the used catalyst in the HC process. The effects of the applied catalyst, pH of the initial solution (1.0-9.7), initial UDMH concentration (2-15 mg/l), inlet pressure (5.5-7.8bar), and downstream pressure (2-6 bar), have been investigated. The results showed that the highest cavitation yield can be obtained at pH 3 and initial UDMH concentration of 10mg/l. Also, an increase in the inlet pressure would lead to an increase in the extent of UDMH degradation. In addition, the optimum value of 3 bar was determined for the downstream pressure that resulted to 98.6% degradation of UDMH after 120 min of processing time. Neither n-nitrosodimethylamine (NDMA) nor any other toxic byproduct (/end-product) was observed in the investigated samples. Formic acid and acetic acid, as well as nitromethane, were identified as oxidation by-products. The present work has conclusively established that hydrodynamic cavitation in combination with Fenton's chemistry can be effectively used for the degradation of UDMH. Copyright © 2014 Elsevier B.V. All rights reserved.

Oxidation products of INCONEL alloys 600 and 690 in pressurized water reactor environments and their role in intergranular stress corrosion cracking

NASA Astrophysics Data System (ADS)

Ferguson, J. B.; Lopez, Hugo F.

2006-08-01

In this work, thermodynamic arguments for the stability of Ni and Cr compounds developed under pressurized water reactor environments ( P_{H_2 O} and P_{H_2 } ) were experimentally tested. A mechanism is proposed to explain crack initiation and propagation alloy 600 along the grain boundaries, where Cr2O3 has formed from the leaching of Cr from the matrix, leaving behind a porous Ni-rich region. The mechanism is based on the thermodynamic potential for the transformation of a protective NiO surface layer into an amorphous nonprotective Ni(OH)2 gel. This gel would also form along the grain boundaries and when hydrogenated steam reaches the porous Ni-rich regions. Crack initiation is then favored by tensile stressing of the grain boundary regions, which can easily rupture the gelatinous film. The leaching of matrix Cr to form nonprotective CrOOH gel at the crack tip followed by the exposure of fresh porous Ni to the environment could explain crack propagation in INCONEL alloy 600. The proposed crack initiation mechanism is not expected to occur in alloy 690 where a protective Cr2O3 film covers the entire metal surface. However, crack propagation along the grain boundaries in alloy 600 and precracked alloy 690 is expected to be active as hydroxide-forming reactions weaken the boundaries.

Chitosan-rectorite nanospheres immobilized on polystyrene fibrous mats via alternate electrospinning/electrospraying techniques for copper ions adsorption

NASA Astrophysics Data System (ADS)

Tu, Hu; Huang, Mengtian; Yi, Yang; Li, Zhenshun; Zhan, Yingfei; Chen, Jiajia; Wu, Yang; Shi, Xiaowen; Deng, Hongbing; Du, Yumin

2017-12-01

Chitosan (CS), as a kind of well characterized biopolymer, has been used for heavy metal adsorption due to its low cost and high efficacy. However, when used directly, chitosan particles had small surface area and weak mechanical strength which is unfavorable to metal adsorption and reused. Besides, it cannot be easily recycled that may cause a secondary pollution. In this paper, CS and layered silicate rectorite (REC) were fully mixed and the mixtures were subsequently electrosprayed nano-sized spheres, which were immobilized on the surface of electrospun polystyrene (PS) mats for metal adsorption. The morphology analysis taken from SEM confirmed that CS-REC nanospheres were loaded on the surface of PS fibrous mats. Small Angle X-ray diffraction patterns showed that the interlayer distance of REC in composite mats was enlarged by the intercalation of CS chains; such structure meant bigger surface area which was helpful for metal adsorption. The data of contact angle implied that PS mats coated with CS-REC nanospheres exhibited better hydrophilicity than PS mats, which was conductive to adsorption rate. Besides, the copper ions adsorption of composite mats was tested at different conditions including the adsorption time, the initial pH and the initial concentration of copper ion. The results demonstrated that PS mats coated with CS-REC nanospheres had the adsorption capacity up to 134 mg/g. In addition, the addition of REC containing Ca2+ could also improve the metal adsorption because of cation exchange. The desorption assay indicated that PS mats immobilized with CS and CS-REC still kept high adsorption ability which retained 74% and 78% after three adsorption-desorption cycles.

Marble waste and pig manure amendments decrease metal availability, increase soil quality and facilitate vegetation development in bare mine soils

NASA Astrophysics Data System (ADS)

Zornoza, Raúl; Faz, Ángel; Martínez-Martínez, Silvia; Acosta, José A.; Gómez, M. Dolores; Ángeles Muñoz, M.

2013-04-01

In order to bring out a functional and sustainable land use in a highly contaminated mine tailing, firstly environmental risks have to be reduced or eliminated by suitable reclamation activities. Tailing ponds pose environmental hazards, such as acidity and toxic metals reaching to waters through wind and water erosions and leaching. As a consequence, soils have no vegetation and low soil organic matter and nutrients. Various physicochemical and biochemical properties, together with exchangeable metals were measured before, 6 months and 12 months after the application of marble waste and pigs manure as reclamation strategy in a tailing pond from SE Spain to reduce hazards for environment and human health. Three months after the last addition of amendments, eight different native shrub species where planted for phytostabilization. Results showed the pH increased up to neutrality. Aggregates stability, organic carbon, total nitrogen, cation exchange capacity, bioavailable phosphorus and potassium, microbial biomass and microbial activity increased with the application of the amendments, while exchangeable metals drastically decreased (~90%). After one year of plantation, only 20% planted species died, with a high growth of survivals reaching flowering and fructification. This study confirms the high effectiveness of initial applications of marble wastes together with pig manure and plantation of shrub species to initialize the recovery of the ecosystem in bare mine soils under Mediterranean semiarid conditions. Key Words: pig manure, marble waste, heavy metals, mine soil. Acknowledgements This work has been funded by the European Union LIFE+ project MIPOLARE (LIFE09 ENV/ES/000439). J.A. Acosta acknowledges a "Saavedra Fajardo" contract from Comunidad Autónoma de Murcia (Spain)

The influence of electrode type on electrocoagulation process for removal of chromium (VI) metal in plating industrial wastewater

NASA Astrophysics Data System (ADS)

Prasetyaningrum, Aji; Jos, Bakti; Dharmawan, Yudhy; Prabowo, Bilal T.; Fathurrazan, Muh.; Fyrouzabadi

2018-05-01

Chromium (VI) is one of the major metallic pollutants in plating industrial wastewater. Cr(VI) is one of toxic metal that cause serious threat to human health and the environment because its non-biodegradable. Among the technologies for removing these pollutants, electrocoagulation can be considered as an effective method. This method have some advantages such as less amount of produced sludge and high efficiency in removal of pollutants.This research intended to study the effects of type of electrode on the degree of Cr(VI) removal from wastewater of plating industry using electrocoagulation method. This laboratory research conducted with 3 types of electrode (aluminum, stainless and combination of both electrode). Synthetic chromium wastewater was prepared at the initial concentration of 100 mg L-1. The process was conducted at pH 3. The electricity current was setting at 3 Ampere. The variable of time of electrocoagulation at 1 and 2 hours. After performing the process on electrochemical cells, samples analyzed by the UV-Vis spectrophotometer regarding amount of Cr(VI) metals. The results showed that aluminium was the best performance electrode at variable of 2 hours with 26% of reduction of Cr(VI)metal content in plating industrial waste water.

Metal/Metal Oxide Differential Electrode pH Sensors

NASA Technical Reports Server (NTRS)

West, William; Buehler, Martin; Keymeulen, Didier

2007-01-01

Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

The pH-dependent leaching behavior of slags from various stages of a copper smelting process: Environmental implications.

PubMed

Jarošíková, Alice; Ettler, Vojtěch; Mihaljevič, Martin; Kříbek, Bohdan; Mapani, Ben

2017-02-01

The leaching behaviors of primary copper (Cu) slags originating from Ausmelt, reverbatory, and converter furnaces operating under a single technological process were compared to a residual slag tailing obtained by slag re-processing via flotation and metal recovery. The EN 12457-2 leaching test, used for assessment of the hazardous properties, was followed by the CEN/TS 14997 pH-static leaching test (pH range 3-12). Both leaching experiments were coupled with a mineralogical investigation of the primary and secondary phases as well as geochemical modeling. Metals (Cd, Cu, Pb, Zn) exhibit the highest leaching at low pH. Under acidic conditions (pH 3-6), Ausmelt slag and slag tailing exhibited higher metal leaching compared to other slag types. Very low leaching of metals (far below EU limits for non-hazardous waste) was observed at natural pH (7.9-9.0) for all the studied slag samples. In contrast, relatively high leaching of As was observed over the entire pH range, especially for Ausmelt slag (exceeding the EU limit for hazardous waste by 1.7×). However, geochemical modeling and scanning electron microscopy indicated that formation of stable Ca-Cu-Pb arsenates and the binding of As to newly formed Fe (oxyhydr)oxides play an important role in efficient As immobilization at the slag-water interface. In contrast, no controls were predicted for Sb, whose leaching was almost pH-independent. Nevertheless Sb leached concentrations at natural pH were below EU limit for hazardous waste. Re-processing of primary Cu slags for metal recovery, and subsequent co-disposal of the resulting slag tailing with dolomite-rich mine tailing and local laterite is suitable for stabilizing the remaining contaminants (except Sb) and limiting their leaching into the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Heavy metals in MSW incineration fly ashes

NASA Astrophysics Data System (ADS)

Ferreira, C.; Ribeiro, A.; Ottosen, L.

2003-05-01

Incineration is a common solution for dealing with the increasing amount of municipal solid waste (MSW). During the process, the heavy metals initially present in the waste go through several transformations, ending up in combustion products, such as fly ash. This article deals with some issues related to the combustion of MSW and the formation of fly ash, especially in what concerns heavy metals. Treatment of the flue gas in air pollution control equipment plays an important role and the basic processes to accomplish this are explained. Fly ash from a semi-dry flue gas treatment system is characterized regarding its physical-chemical properties: pH, solubility, chemical composition, and leaching, amongst others. Results indicate a high alkalinity and the presence of large amounts of calcium, chlorides, sulfates, carbonates, sodium and potassium. Metal concentrations in fly ash are: 6,2g/kg for zinc, 2,4g/kg for lead, 1,7g/kg for iron, and 7,9g/kg for magnesium. Copper, manganese, chromium and cadmium are also present with 546, 338, 104 and 91mg/kg of fly ash, respectively. These results are extremely important in subsequent studies on the treatment of fly ash.

The Role of Hydroxide and Metal Concentration on the Viscoelastic Properties of Metal Coordinated Gels

NASA Astrophysics Data System (ADS)

Cazzell, Seth; Holten-Andersen, Niels

Nature uses metal binding amino acids to engineer mechanical properties. An example of this engineering can be found in the mussel byssal thread. This acellular thread contains reversible intermolecular protein-metal bonds, which allows the mussel to robustly anchor to rocks, while withstanding the mechanically demanding intertidal environment. Inspired by this metal-binding material, we present a synthetic hydrogel designed to mimic this bonding behavior. The mechanical properties of this hydrogel can be controlled independently by manipulating the amount of metal relative to the metal binding ligand, and the gel's pH. Here we report how high metal to ligand ratios and low pH can be used to induce the formation of a strong, slow relaxing gels. This gel has potential applications as an energy dissipating material, and furthers our understanding of the bio-inspired engineering techniques that are used to design viscoelastic soft materials. I was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

Mode suppression in metal filled photonic crystal vertical cavity lasers

NASA Astrophysics Data System (ADS)

Griffin, Benjamin G.; Arbabi, Amir; Goddard, Lynford L.

2012-03-01

Simulation results for an etched air hole photonic crystal (PhC) vertical cavity surface emitting laser (VCSEL) structure with various thicknesses of metal deposited inside the holes are presented. The higher-order modes of the structure are more spread out than the fundamental mode, and penetrate into the metal-filled holes. Due to the lossy nature of the metal, these higher-order modes experience a greater loss than the fundamental mode, resulting in an enhanced side mode suppression ratio (SMSR). A figure of merit for determining which metals would have the greatest impact on the SMSR is derived and validated using a transmission matrix method calculation. A full three-dimensional simulation of the PhC VCSEL structure is performed using the plane wave admittance method, and SMSRs are calculated for increasing metal thicknesses. Of the metals simulated, chromium provided the greatest SMSR enhancement with more than a 4 dB improvement with 500 nm of metal for an operating current of 12 times threshold.

Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: II. Some general geologic applications

USGS Publications Warehouse

Hemley, J.J.; Hunt, J.P.

1992-01-01

The experimental metal solubilities for rock-buffered hydrothermal systems provide important insights into the acquisition, transport, and deposition of metals in real hydrothermal systems that produced base metal ore deposits. Water-rock reactions that determine pH, together with total chloride and changes in temperature and fluid pressure, play significant roles in controlling the solubility of metals and determining where metals are fixed to form ore deposits. Deposition of metals in hydrothermal systems occurs where changes such as cooling, pH increase due to rock alteration, boiling, or fluid mixing cause the aqueous metal concentration to exceed saturation. Metal zoning results from deposition occurring at successive saturation surfaces. Zoning is not a reflection simply of relative solubility but of the manner of intersection of transport concentration paths with those surfaces. Saturation surfaces will tend to migrate outward and inward in prograde and retrograde time, respectively, controlled by either temperature or chemical variables. -from Authors

Deconvolution of the role of metal and pH in metal coordinating polymers

NASA Astrophysics Data System (ADS)

Cazzell, Seth; Holten-Andersen, Niels

Nature uses metal binding amino acids to engineer both mechanical properties and structural functionality. Some examples of this metal binding behavior can be found in both mussel foot protein and DNA binding protein. The mussel byssal thread contains reversible intermolecular protein-metal bonds, allowing it to withstand harsh intertidal environments. Zinc fingers form intramolecular protein-metal bonds to stabilize the tertiary structure of DNA binding proteins, allowing specific structural functionality. Inspired by both these metal-binding materials, we present mechanical and spectroscopic characterization of a model polymer system, designed to mimic this bonding. Through these studies, we are able to answer fundamental polymer physics questions, such as the role of pH and metal to ligand ratio, illuminating both the macroscopic and microscopic material behavior. These understandings further bio-inspired engineering techniques that are used to design viscoelastic soft materials. I was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

Simultaneous removal of As, Cd, Cr, Cu, Ni and Zn from stormwater using high-efficiency industrial sorbents: Effect of pH, contact time and humic acid.

PubMed

Genç-Fuhrman, Hülya; Mikkelsen, Peter S; Ledin, Anna

2016-10-01

The effect of contact time, solution pH, and the presence of humic acid (HA) on the combined removal of As, Cd, Cr, Cu, Ni and Zn is investigated in batch tests using alumina, granulated activated carbon (GAC), and bauxsol coated sand (BCS) as sorbents. It is found that the equilibrium time for Cd, Cu, Ni and Zn is about 4h, while no clear equilibrium is observed for As and Cr. It is also found that increasing the pH until pH~8 enhanced Cd, Cu, Ni and Zn removal, but increasing the pH above this point had no major effect. In the cases of As and Cr, higher pH values (i.e. >7) decreased their removal. The presence of both 20 and 100mg/L HA suppressed the heavy metal removal except for Cr, and the suppression was higher at the higher HA concentration. Geochemical simulations suggest that this is due to the formation of dissolved HA-metal complexes preventing effective metal sorption. In the case of Cr, the presence of HA increased the removal when using alumina or BCS, while hindering the removal when using GAC. The findings show that the pH-value of the stormwater to be treated must be in the range of 6-7 in order to achieve removal of the full spectrum of metals. The results also show that natural organic matter may severely influence the removal efficiency, such that, for most metals the removal was reduced to the half, while for Cr it was increased to the double for alumina and BCS. Consequently, a properly working filter set up may not work properly anymore when receiving high loads of natural organic acids during the pollen season in spring or during defoliation in autumn and early winter, and during mixing of runoff with snowmelt having a low pH. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of indian mustard (Brassica juncea) on rhizosphere soil solution chemistry in long-term contaminated soils: a rhizobox study.

PubMed

Kim, Kwon-Rae; Owens, Gary; Kwon, Soon-lk

2010-01-01

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four different types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17-156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst different soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.

Solution and particle effects on the biosorption of heavy metals by seaweed biomass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leusch, A.; Holan, Z.R.; Volesky, B.

Biosorption of cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) by six fractions of particle sizes, ranging from 0.063 to 1.4 mm of dry marine algal biomass of Sargassum fluitans and Ascophyllum nodosum, is examined. Equilibrium metal uptake by larger particles was higher than that by smaller particles in the order of Pb > Cd > Cu > Co > Zn > Ni for both biomass types, with S. fluitans sorbing slightly more than A. nodosum. Uptakes of metals ranged from the highest, q{sub max} = 369 mg Pb/g (particle size 0.84-1.00 mm), to themore » low Zn and Ni uptakes, q{sub max} = 77 mg/g (size 0.84-1.00 mm) for S. fluitans. A. nodosum adsorbed metals in the range from q{sub max} = 287 mg Pg/g (particle size 0.84-1.00 mm) to q{sub max} = 73 mg Zn/g (particle size 0.84-1.00mm). Harder stipe fractions of S. fluitans demonstrated generally higher metal uptakes than the softer fractions derived from its blades (leaves). The pH dependence of the Zn uptake by S. fluitans exhibited an S-shaped curve between pH 1.5 and pH 7, with 50% of the maximum (pH 7.0) uptake at pH 3.5. Monovalent Na and K ions at higher concentrations inhibited the biosorption of Zn by S. fluitans. A significant inhibition started at 50 mM potassium chloride or sodium acetate, and at 1M the biosorption was completely blocked. 40 refs., 8 figs., 3 tabs.« less

Molecular binding mechanisms of aqueous cadmium and lead to siderophores, bacteria and mineral surfaces

NASA Astrophysics Data System (ADS)

Mishra, Bhoopesh

Recent studies have shown that diverse groups of bacteria adsorb metals to similar extents and uptake can be modeled using a universal adsorption model. In this study, XAFS has been used to resolve whether binding sites determined for single species systems are responsible for adsorption in more complex natural bacterial assemblages. Results obtained from a series of XAFS experiments on pure Gram positive and Gram negative bacterial strains and consortia of bacteria as a function of pH and Cd loading suggests that every bacterial strain has a complex physiology and they are all slightly different from each other. Nevertheless from the metal adsorption chemistry point of view, the main difference between them lies in the site ratio of three fundamental sites only - carboxyl, phosphoryl and sulfide. Two completely different consortia of bacteria (obtained from natural river water, and soil system with severe organic contamination) were successfully modeled in the pH range 3.4--7.8 using the EXAFS models developed for single species systems. Results thus obtained can potentially have very high impact on the modeling of the complex bacterial systems in realistic geological settings, leading to further refinement and development of robust remediation strategies for metal contamination at macroscopic level. In another study, solution speciation of Pb and Cd with DFO-B has been examined using a combination of techniques (ICP, TOC, thermodynamic modeling and XAFS). Results indicate that Pb does not complex with DFO-B at all until about pH 3.5, but forms a totally caged structure at pH 7.5. At intermediate pH conditions, mixture of species (one and two hydroxamate groups complexed) is formed. Cd on the other hand, does not complex until pH 5, forms intermediate complexes at pH 8 and is totally chelated at pH 9. Further studies were conducted for Pb sorption to mineral surface kaolinite with and without DFO-B. In the absence of DFO-B, results suggest outer sphere and inner sphere sorption of Pb on kaolinite surface at acidic and circumneutral pH conditions respectively. In the presence of DFO-B, bulk sorption studies indicated that Pb sorption is enhanced in the presence of DFO-B around pH 6 and inhibited above pH 6.5. This was confirmed by x-ray fluorescence measurements. Extended XAFS study clearly indicated unwrapping of DFO-B molecule at the surface. Our study has unambiguously recognized it as a "Type A" ternary complex ("Type A" complex means surface-metal-ligand type of interaction). Taken together, bulk adsorption measurements and XAFS experiments represent a powerful approach for determining and modeling metal speciation and adsorption.

The effect of pH on metal accumulation in two Alyssum species.

PubMed

Kukier, Urszula; Peters, Carinne A; Chaney, Rufus L; Angle, J Scott; Roseberg, Richard J

2004-01-01

Nickel phytoextraction using hyperaccumulator plants offers a potential for profit while decontaminating soils. Although soil pH is considered a key factor in metal uptake by crops, little is known about soil pH effects on metal uptake by hyperaccumulator plants. Two Ni and Co hyperaccumulators, Alyssum murale and A. corsicum, were grown in Quarry muck (Terric Haplohemist) and Welland (Typic Epiaquoll) soils contaminated by a Ni refinery in Port Colborne, Ontario, Canada, and in the serpentine Brockman soil (Typic Xerochrepts) from Oregon, USA. Soils were acidified and limed to cover pH from strongly acidic to mildly alkaline. Alyssum grown in both industrially contaminated soils exhibited increased Ni concentration in shoots as soil pH increased despite a decrease in water-soluble soil Ni, opposite to that seen with agricultural crop plants. A small decrease in Alyssum shoot Ni concentration as soil pH increased was observed in the serpentine soil. The highest fraction of total soil Ni was phytoextracted from Quarry muck (6.3%), followed by Welland (4.7%), and Brockman (0.84%). Maximum Ni phytoextraction was achieved at pH 7.3, 7.7, and 6.4 in the Quarry, Welland, and Brockman soils, respectively. Cobalt concentrations in shoots increased with soil pH increase in the Quarry muck, but decreased in the Welland soil. Plants extracted 1.71, 0.83, and 0.05% of the total soil Co from Welland, Quarry, and Brockman, respectively. The differences in uptake pattern of Ni and Co by Alyssum from different soils and pH were probably related to the differences in organic matter and iron contents of the soils.

Ductile failure X-prize.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cox, James V.; Wellman, Gerald William; Emery, John M.

2011-09-01

Fracture or tearing of ductile metals is a pervasive engineering concern, yet accurate prediction of the critical conditions of fracture remains elusive. Sandia National Laboratories has been developing and implementing several new modeling methodologies to address problems in fracture, including both new physical models and new numerical schemes. The present study provides a double-blind quantitative assessment of several computational capabilities including tearing parameters embedded in a conventional finite element code, localization elements, extended finite elements (XFEM), and peridynamics. For this assessment, each of four teams reported blind predictions for three challenge problems spanning crack initiation and crack propagation. After predictionsmore » had been reported, the predictions were compared to experimentally observed behavior. The metal alloys for these three problems were aluminum alloy 2024-T3 and precipitation hardened stainless steel PH13-8Mo H950. The predictive accuracies of the various methods are demonstrated, and the potential sources of error are discussed.« less

Biogenic hydroxyapatite (Apatite II™) dissolution kinetics and metal removal from acid mine drainage.

PubMed

Oliva, J; Cama, J; Cortina, J L; Ayora, C; De Pablo, J

2012-04-30

Apatite II™ is a biogenic hydroxyapatite (expressed as Ca(5)(PO(4))OH) derived from fish bone. Using grains of Apatite II™ with a fraction size between 250 and 500 μm, batch and flow-through experiments were carried out to (1) determine the solubility constant for the dissolution reaction Ca(5)(PO(4))(3)(OH) ⇔ 5Ca(2+) + 3PO(4)(3-) + OH(-), (2) obtain steady-state dissolution rates over the pH range between 2.22 and 7.14, and (3) study the Apatite II™'s mechanisms to remove Pb(2+), Zn(2+), Mn(2+), and Cu(2+) from metal polluted water as it dissolves. The logK(S) value obtained was -50.8±0.82 at 25 °C. Far-from-equilibrium fish-bone hydroxyapatite dissolution rates decrease by increasing pH. Assuming that the dissolution reaction is controlled by fast adsorption of a proton on a specific surface site that dominates through the pH range studied, probably ≡PO(-), followed by a slow hydrolysis step, the dissolution rate dependence is expressed in mol m(-2) s(-1) as where Rate(25 °C) = -8.9 × 10(-10) × [9.96 × 10(5) × a(H+)]/[1 + 9.96 × 10(5) × a(H+)] where a(H+) is the proton activity in solution. Removal of Pb(2+), Zn(2+), Mn(2+) and Cu(2+) was by formation of phosphate-metal compounds on the Apatite II™ substrate, whereas removal of Cd(2+) was by surface adsorption. Increase in pH enhanced the removal of aqueous heavy metals. Using the kinetic parameters obtained (e.g., dissolution rate and pH-rate dependence law), reactive transport simulations reproduced the experimental variation of pH and concentrations of Ca, P and toxic divalent metal in a column experiment filled with Apatite II™ that was designed to simulate the Apatite II™-metal polluted water interaction. Copyright © 2012 Elsevier B.V. All rights reserved.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

Abandoned mine drainage in the Swatara Creek Basin, southern anthracite coalfield, Pennsylvania, USA: 1. stream quality trends coinciding with the return of fish

USGS Publications Warehouse

Cravotta, Charles A.; Brightbill, Robin A.; Langland, Michael J.

2010-01-01

Acidic mine drainage (AMD) from legacy anthracite mines has contaminated Swatara Creek in eastern Pennsylvania. Intermittently collected base-flow data for 1959–1986 indicate that fish were absent immediately downstream from the mined area where pH ranged from 3.5 to 7.2 and concentrations of sulfate, dissolved iron, and dissolved aluminum were as high as 250, 2.0, and 4.7 mg/L, respectively. However, in the 1990s, fish returned to upper Swatara Creek, coinciding with the implementation of AMD treatment (limestone drains, limestone diversion wells, limestone sand, constructed wetlands) in the watershed. During 1996–2006, as many as 25 species of fish were identified in the reach downstream from the mined area, with base-flow pH from 5.8 to 7.6 and concentrations of sulfate, dissolved iron, and dissolved aluminum as high as 120, 1.2, and 0.43 mg/L, respectively. Several of the fish taxa are intolerant of pollution and low pH, such as river chub (Nocomis icropogon) and longnose dace (Rhinichthys cataractae). Cold-water species such as brook trout (Salvelinus fontinalis) and warm-water species such as rock bass (Ambloplites rupestris) varied in predominance depending on stream flow and stream temperature. Storm flow data for 1996–2007 indicated pH, alkalinity, and sulfate concentrations decreased as the stream flow and associated storm-runoff component increased, whereas iron and other metal concentrations were poorly correlated with stream flow because of hysteresis effects (greater metal concentrations during rising stage than falling stage). Prior to 1999, pH\\5.0 was recorded during several storm events; however, since the implementation of AMD treatments, pH has been maintained near neutral. Flow-adjusted trends for1997–2006 indicated significant increases in calcium; decreases in hydrogen ion, dissolved aluminum, dissolved and total manganese, and total iron; and no change in sulfate or dissolved iron in Swatara Creek immediately downstream from the mined area. The increased pH and calcium from limestone in treatment systems can be important for mitigating toxic effects of dissolved metals. Thus, treatment of AMD during the 1990s improved pH buffering, reduced metals transport, and helped to decrease metals toxicity to fish.

Simultaneous removal of aqueous Zn2+, Cu2+, Cd2+, and Pb2+ by zeolites synthesized from low-calcium and high-calcium fly ash.

PubMed

Ji, X D; Ma, Y Y; Peng, S H; Gong, Y Y; Zhang, F

2017-10-01

In this study, zeolites were synthesized from low-calcium (LCZ) and high-calcium (HCZ) fly ash, respectively. Subsequently, the zeolites were tested for their removal effectiveness for four aqueous cations, namely, Zn 2+ , Cu 2+ , Cd 2+ , and Pb 2+ , as a function of contact time, pH value, adsorbent dosage, and initial concentration of heavy metals. Both zeolites were characterized by X-ray diffraction, X-ray fluorescence spectrometry, scanning electron microscopy, specific surface area, and cation exchange capacity. The results show that HCZ mainly consists of an unnamed zeolite (Na 6 [AlSiO 4 ] 6 ·4H 2 O), whereas LCZ mainly consists of faujasite-type zeolite. The optimum sorption conditions were pH = 6.0; adsorbent dosage = 1.0 g·L -1 ; temperature = 25 °C; contact time = 100 min; and initial heavy metal concentration = 100 mg·L -1 . The sorption kinetics of the four aqueous cations on both LCZ and HCZ followed the pseudo-second-order kinetic model, and the sorption isotherm data fitted well with the Langmuir isotherm model. For LCZ, the maximum adsorption capacities of Zn 2+ , Cu 2+ , Cd 2+ , and Pb 2+ were 155.76, 197.86, 123.76, and 186.22 mg·g -1 , respectively. For HCZ, the values were 154.08, 183.15, 118.91, and 191.94 mg·g -1 , respectively. The zeolites were regenerated by NaCl solution (1 mol·L -1 ) and showed high removal efficiency. In conclusion, zeolites produced by fly ash are promising materials for removing Zn 2+ , Cu 2+ , Cd 2+ , and Pb 2+ from wastewater.

Role of multiple substrates (spent mushroom compost, ochre, steel slag, and limestone) in passive remediation of metal-containing acid mine drainage.

PubMed

Molahid, Verma Loretta M; Mohd Kusin, Faradiella; Madzin, Zafira

2018-01-12

The potential of selected materials in treating metal-rich acid mine drainage (AMD) has been investigated in a series of batch experiment. The efficiencies of both single and mixed substrates under two conditions i.e. low- and high-concentration solutions containing heavy metals were evaluated. Synthetic metal-containing AMD was used in the experiments treated using spent mushroom compost (SMC), ochre, steel slag (SS), and limestone. Different ratios of treatment materials were incorporated in the substrate mix and were tested in an anoxic condition. In the batch test, physicochemical parameters (pH, redox potential, total dissolved solids, conductivity, and Ca concentration) and heavy metals (Fe, Mn, Pb, Zn, and Al) were analysed. The mixed substrates have shown satisfactory performance in increasing pH with increasing Ca concentration and removing metals. It has been found that SS and ochre played an important role in the treatment of AMD. The results showed that the mixed substrates SM1 (i.e. 10% SMC mixed with 20% ochre, 30% steel slag, and 40% limestone) and SM2 (i.e. 20% SMC mixed with 30% ochre, 40% steel slag, and 10% limestone) were effective in increasing the pH from as low as 3.5-8.09, and removing heavy metals with more than 90% removal efficiencies.

Macroalgal biomonitors of trace metal contamination in acid sulfate soil aquaculture ponds.

PubMed

Gosavi, K; Sammut, J; Gifford, S; Jankowski, J

2004-05-25

Earthen shrimp aquaculture ponds are often impacted by acid sulfate soils (ASS), typically resulting in increased disease and mortality of cultured organisms. Production losses have been attributed to either low pH or to elevated concentrations of toxic metals, both direct products of pyrite oxidation in ASS. The standard farm management practice to minimise effects of pyrite oxidation is to maintain pH of pond waters above 5, based on the assumption that dissolved metal bioavailability is negligible at this pH. This study aimed to test the validity of this assumption, and therefore elucidate a possible role of toxic heavy metals in observed decreases in farm productivity. Metal bioaccumulation in four genera of macroalgae, Ulva sp., Enteromorpha sp., Cladophora sp. and Chaetomorpha sp., sampled from ASS-affected shrimp aquaculture ponds were measured using inductively coupled plasma-optical emission spectroscopy (ICP-OES) to assess the relative bioavailability of dissolved metals within the system. Results showed that all four genera of macroalgae accumulated appreciable quantities of Fe, Al, Zn, Cd, Cu, As and Pb. Iron and Al, the most common metals mobilised from ASS, were both accumulated in all algal genera to concentrations three orders of magnitude greater than all other metals analysed. These findings indicate that dissolved heavy metals are indeed bioavailable within the aquaculture pond system. A literature search of heavy metal bioaccumulation by these algal genera revealed concentrations recorded in this study are comparable to highly contaminated environments, such as those exposed to urban, industrial and mining pollution. The results of this study indicate that dissolved metal bioavailability in many earthen shrimp aquaculture ponds may be higher than previously thought.

Adsorption of divalent metals to metal oxide nanoparicles: Competitive and temperature effects

NASA Astrophysics Data System (ADS)

Grover, Valerie Ann

The presence of metals in natural waters is becoming a critical environmental and public health concern. Emerging nanotechnology and the use of metal oxide nanoparticles has been identified as a potential remediation technique in removing metals from water. However, practical applications are still being explored to determine how to apply their unique chemical and physical properties for full scale remediation projects. This thesis investigates the sorption properties of Cd(II), Cu(II), Pb(II) and Zn(II) to hematite (alpha-Fe2O3) and titanium dioxide (TiO2) nanoparticles in single- and binary-adsorbate systems. Competitive sorption was evaluated in 1L batch binary-metal systems with 0.05g/L nano-hematite at pH 8.0 and pH 6.0. Results indicate that the presence of a secondary metal can affect the sorption process depending upon the molar ratios, such as increased or reduced adsorption. Thermodynamic properties were also studied in order to better understand the effects of temperature on equilibrium and kinetic adsorption capabilities. Understanding the thermodynamic properties can also give insight to determine if the sorption process is a physical, chemical or ion exchange reaction. Thermodynamic parameters such as enthalpy (DeltaH), entropy (DeltaS), and Gibbs free energy (DeltaG) were evaluated as a function of temperature, pH, and metal concentration. Results indicate that Pb(II) and Cu(II) adsorption to nano-hematite was an endothermic and physical adsorption process, while Zn(II) and Cd(II) adsorption was dependent upon the adsorbed concentration evaluated. However, metal adsorptions to nano-titanium dioxide were all found to be endothermic and physical adsorption processes; the spontaneity of metal adsorption was temperature dependent for both metal oxide nanoparticles.

Interaction of Cu(+) with cytosine and formation of i-motif-like C-M(+)-C complexes: alkali versus coinage metals.

PubMed

Gao, Juehan; Berden, Giel; Rodgers, M T; Oomens, Jos

2016-03-14

The Watson-Crick structure of DNA is among the most well-known molecular structures of our time. However, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or the presence of cations. Pairing of cytosine (C) bases induced by the sharing of a single proton (C-H(+)-C) may give rise to the so-called i-motif, which occurs primarily in expanded trinucleotide repeats and the telomeric region of DNA, particularly at low pH. At physiological pH, silver cations were recently found to stabilize C dimers in a C-Ag(+)-C structure analogous to the hemiprotonated C-dimer. Here we use infrared ion spectroscopy in combination with density functional theory calculations at the B3LYP/6-311G+(2df,2p) level to show that copper in the 1+ oxidation state induces an analogous formation of C-Cu(+)-C structures. In contrast to protons and these transition metal ions, alkali metal ions induce a different dimer structure, where each ligand coordinates the alkali metal ion in a bidentate fashion in which the N3 and O2 atoms of both cytosine ligands coordinate to the metal ion, sacrificing hydrogen-bonding interactions between the ligands for improved chelation of the metal cation.

Unravelling metal mobility under complex contaminant signatures.

PubMed

de Souza Machado, Anderson Abel; Spencer, Kate L; Zarfl, Christiane; O'Shea, Francis T

2018-05-01

Metals are concerning pollutants in estuaries, where contamination can undergo significant remobilisation driven by physico-chemical forcing. Environmental concentrations of metals in estuarine sediments are often higher than natural backgrounds, but show no contiguity to potential sources. Thus, better understanding the metal mobility in estuaries is essential to improve identification of pollution sources and their accountability for environmental effects. This study aims to identify the key biogeochemical drivers of metal mobilisation on contaminated estuarine sediments through (1) evaluation of the potential mobilisation under controlled conditions, and (2) investigation of the relevance of metal mobilisation for in situ pollution levels in an area with multiple contaminant sources. Sediments from a saltmarsh adjacent to a coastal landfill, a marina, and a shipyard on the Thames Estuary (Essex, UK) were exposed in the laboratory (24h, N=96, 20°C) to water under various salinity, pH, and redox potential. Major cations, Fe(II), and trace metal concentrations were analysed in the leachate and sediment. Salinity, pH and redox had a significant effect on metal mobilisation (p<0.001), e.g. under certain conditions Fe(II) leaching was increased ~1000-fold. Measurements in situ of surface and subsurface sediment cores revealed that landfill proximity poorly explained metal spatial distribution. However, physicochemical parameters explained up to 97% of geochemically normalized metal concentrations in sediments. Organic matter and pH were dominant factors for most of the metal concentrations at the sediment surface. At subsurface, major cations (Ca, Na, Mg and K) were determinant predictors of metal concentrations. Applying the empirical model obtained in the laboratory to geochemical conditions of the studied saltmarsh it was possible to demonstrate that Fe mobilisation regulates the fate of this (and other) metal in that area. Thus, present results highlight the importance of metal mobility to control sediment pollution and estuarine fate of metals. Copyright © 2017 Elsevier B.V. All rights reserved.

Reducible oxide based catalysts

DOEpatents

Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

2010-04-06

A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

[Biosorption of heavy metals in fluoritum decoction by fungal mycelium].

PubMed

Cui, Pei-wu; Hu, Wei; Hu, Ya-qiang; Tan, Zhao-yang

2014-09-01

To explore the biosorption technology of heavy metals in Fluoritum decoction by fungal mycelium. Four factors including fungal mycelium amount, adsorption time, pH value and temperature were employed to estimate the fungal biomass adsorption conditions for removing the heavy metals in Fluoritum decoction. Then an orthogonal experimental design was taken to optimize the biosorption process, and the removal efficiency was also evaluated. Under the optimized conditions of 1.0 g/50 mL Fluoritum decoction, 3 hours adsorption time, pH 5.0 and 40 degrees C, a result of 70.12% heavy metals removal rate was accomplished with 35.99% calcium ion loss. The study indicates that removing of heavy metals in Fluoritum decoction through fungal mycelium is feasible, and the experiment results can also provide a basis for further research on biosorption of heavy metals in traditional Chinese medicine

Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

NASA Astrophysics Data System (ADS)

Marzouk, E. R.; Chenery, S. R.; Young, S. D.

2013-12-01

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

Study of the uptake by duckweed of aluminum, copper, and lead from aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, S.C.; Choi, D.S.; Robinson, J.W.

1988-01-01

THE UPTAKE OF AL/sup 3 +/, CU/sup 2 +/, AND PB/sup 2 +/ FROM AQUEOUS SOLUTION BY DUCKWEED HAS BEEN OBSERVED AT PH 4.0, 4.5, AND 5.0. THE RESULTS SHOWED THAT THE UPTAKE OF PB/sup 2 +/ WAS MUCH FASTER THAN AL/sup 3 +/ AND CU/sup 2 +/. THE UPTAKE OF CU/sup 2 +/ WAS SUPPRESSED BY THE PRESENCE OF PB/sup 2 +/ AND AL/sup 3 +/. THE PROPORTION OF METAL UPTAKE (PMUT) BY DUCKWEED WAS DEPENDENT ON THE METAL CONCENTRATION IN THE SOLUTION WHEN ONLY ONE KIND OF METAL ION WAS PRESENT. IT WAS DECREASED BY INCREASING CONCENTRATIONS OFmore » OTHER METALS IN MIXTURES OF SOLUTIONS. THE METAL UPTAKE BY THE DUCKWEED WAS ALWAYS LESS THAN THE LOSS OF METAL CONTENT IN THE RELEVANT SOLUTION. THIS FACT IMPLIED THAT THE PROCESS OF THE UPTAKE OF METAL IONS BY THE DUCKWEED MAY INVOLVE TWO STAGES. IN THE FIRST, THE METAL IS ABSORBED BUT THEN LATER IT IS ADSORBED BY THE DUCKWEED. THE ALUMINUM ION WAS FOUND TO BE MORE TOXIC THAN THE COPPER ION AT LOWER PH AND HIGHER CONCENTRATION, BUT THE SITUATION IS REVERSED AT HIGHER PH. A POSSIBLE EXPLANATION OF TOXICITY OF CU/sup 2 +/ AND AL/sup 3 +/ IN CHLOROPHYLL WAS REPLACED BY THE CU/sup 2 +/ OR AL/sup 3 +/. THIS MAY LEAD THE CHLOROPHYLL TO LOSE ITS NORMAL ACTIVITY AND KILL THE DUCKWEED.« less

Pollution control and metal resource recovery for low grade automobile shredder residue: a mechanism, bioavailability and risk assessment.

PubMed

Singh, Jiwan; Lee, Byeong-Kyu

2015-04-01

Automobile shredder residue (ASR) is considered as hazardous waste in Japan and European countries due to presence of heavy metals. This study was carried on the extraction characteristics of heavy metals (Mn, Fe, Ni, and Cr) from automobile shredder residue (ASR). The effects of pH, temperature, particle size, and liquid/solid ratio (L/S) on the extraction of heavy metals were investigated. The recovery rate of Mn, Fe, Ni, and Cr increased with increasing extraction temperature and L/S ratio. The lowest pH 2, the highest L/S ratio, and the smallest particle size showed the highest recovery of heavy metals from ASR. The highest recovery rates were in the following order: Mn > Ni > Cr > Fe. Reduction of mobility factor for the heavy metals was observed in all the size fractions after the recovery. The results of the kinetic analysis for various experimental conditions supported that the reaction rate of the recovery process followed a second order reaction model (R(2) ⩾ 0.95). The high availability of water-soluble fractions of Mn, Fe, Ni, and Cr from the low grade ASR could be potential hazards to the environment. Bioavailability and toxicity risk of heavy metals reduced significantly with pH 2 of distilled water. However, water is a cost-effective extracting agent for the recovery of heavy metals and it could be useful for reducing the toxicity of ASR. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dual-Emitting Fluorescent Metal-Organic Framework Nanocomposites as a Broad-Range pH Sensor for Fluorescence Imaging.

PubMed

Chen, Haiyong; Wang, Jing; Shan, Duoliang; Chen, Jing; Zhang, Shouting; Lu, Xiaoquan

2018-05-15

pH plays an important role in understanding physiological/pathologic processes, and abnormal pH is a symbol of many common diseases such as cancer, stroke, and Alzheimer's disease. In this work, an effective dual-emission fluorescent metal-organic framework nanocomposite probe (denoted as RB-PCN) has been constructed for sensitive and broad-range detection of pH. RB-PCN was prepared by encapsulating the DBI-PEG-NH 2 -functionalized Fe 3 O 4 into Zr-MOFs and then further reacting it with rhodamine B isothiocyanates (RBITC). In RB-PCN, RBITC is capable of sensing changes in pH in acidic solutions. Zr-MOFs not only enrich the target analyte but also exhibit a fluorescence response to pH changes in alkaline solutions. Based on the above structural and compositional features, RB-PCN could detect a wide range of pH changes. Importantly, such a nanoprobe could "see" the intracellular pH changes by fluorescence confocal imaging as well as "measure" the wider range of pH in actual samples by fluorescence spectroscopy. To the best of our knowledge, this is the first time a MOF-based dual-emitting fluorescent nanoprobe has been used for a wide range of pH detection.

Acidithiobacillus ferrooxidans metabolism: from genome sequence to industrial applications

PubMed Central

Valdés, Jorge; Pedroso, Inti; Quatrini, Raquel; Dodson, Robert J; Tettelin, Herve; Blake, Robert; Eisen, Jonathan A; Holmes, David S

2008-01-01

Background Acidithiobacillus ferrooxidans is a major participant in consortia of microorganisms used for the industrial recovery of copper (bioleaching or biomining). It is a chemolithoautrophic, γ-proteobacterium using energy from the oxidation of iron- and sulfur-containing minerals for growth. It thrives at extremely low pH (pH 1–2) and fixes both carbon and nitrogen from the atmosphere. It solubilizes copper and other metals from rocks and plays an important role in nutrient and metal biogeochemical cycling in acid environments. The lack of a well-developed system for genetic manipulation has prevented thorough exploration of its physiology. Also, confusion has been caused by prior metabolic models constructed based upon the examination of multiple, and sometimes distantly related, strains of the microorganism. Results The genome of the type strain A. ferrooxidans ATCC 23270 was sequenced and annotated to identify general features and provide a framework for in silico metabolic reconstruction. Earlier models of iron and sulfur oxidation, biofilm formation, quorum sensing, inorganic ion uptake, and amino acid metabolism are confirmed and extended. Initial models are presented for central carbon metabolism, anaerobic metabolism (including sulfur reduction, hydrogen metabolism and nitrogen fixation), stress responses, DNA repair, and metal and toxic compound fluxes. Conclusion Bioinformatics analysis provides a valuable platform for gene discovery and functional prediction that helps explain the activity of A. ferrooxidans in industrial bioleaching and its role as a primary producer in acidic environments. An analysis of the genome of the type strain provides a coherent view of its gene content and metabolic potential. PMID:19077236

Screening and production of a potent extracellular Arthrobacter creatinolyticus urease for determination of heavy metal ions.

PubMed

Ramesh, Rajendran; Aarthy, Mayilvahanan; Gowthaman, Marichetti Kuppuswami; Gabrovska, Katya; Godjevargova, Tzonka; Kamini, Numbi Ramudu

2014-04-01

This paper describes the isolation of a potent extracellular urease producing microorganism, identified by 16S rRNA as Arthrobacter creatinolyticus MTCC 5604 and its medium optimization by classical one-factor-at-a-time method and central composite rotatable design (CCRD), a tool of response surface methodology (RSM). An optimal activity of 9.0 U ml(-1) was obtained by classical method and statistical optimization of the medium resulted in an activity of 17.35 U ml(-1) at 48 h and 30 °C. This activity was 4.91 times greater than the initial activity (3.53 U ml(-1) ) from the basal medium and the enzyme showed maximum activity at pH 8.0 and 60 °C and was stable at pH 7.0-9.0 and temperatures up to 50 °C. Furthermore, the enzyme was assessed for its activity reduction by determining the inhibitory concentration (IC50 ) of heavy metal ions and the inhibition of urease was in the order of Cu(II) > Cd(II) > Zn(II) > Ni(II). Urease was highly sensitive to Cu(II) and its inhibition was 94% and 100% in model solutions containing a mixture of Cu(II) with heavy metal ions Cd(II) and Zn(II), respectively. The results of these studies suggested that the enzyme could be utilized as sensors to determine the levels of Cu(II) ions in industrial effluents, contaminated soil and ground water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Major factors influencing bacterial leaching of heavy metals (Cu and Zn) from anaerobic sludge.

PubMed

Couillard, D; Chartier, M; Mercier, G

1994-01-01

Anaerobically digested sewage sludges were treated for heavy metal removal through a biological solubilization process called bacterial leaching (bioleaching). The solubilization of copper and zinc from these sludges is described in this study: using continuously stirred tank reactors with and without sludge recycling at different mean hydraulic residence times (1, 2, 3 and 4 days). Significant linear equations were established for the solubilization of zinc and copper according to relevant parameters: oxygen reduction potential (ORP), pH and residence time (t). Zinc solubilization was related to the residence time with a r2 (explained variance) of 0.82. Considering only t=2 and 3 days explained variance of 0.31 and 0.24 were found between zinc solubilization as a function of ORP and pH indicating a minor importance of those two factors for this metal in the range of pH and ORP experimented. Cu solubilization was weakly correlated to mean hydraulic residence time (r2=0.48), while it was highly correlated to ORP (r2=0.80) and pH (r2=0.62) considering only t of 2 and 3 days in the case of pH and ORP. The ORP dependence of Cu solubilization has been clearly demonstrated in this study. In addition to this, the importance of the substrate concentration for Cu solubilization has been confirmed. The hypothesis of a biological solubilization of Cu by the indirect mechanism has been supported. The results permit, under optimum conditions, the drawing of linear equations which will allow prediction of metal solubilization efficiencies from the parameters pH (Cu), ORP (Cu) and residence time (Cu and Zn), during the treatment. The linear regressions will be a useful tool for routine operation of the process.

Toxicity of Pb and of Pb/Cd combination on the springtail Folsomia candida in natural soils: reproduction, growth and bioaccumulation as indicators.

PubMed

Bur, T; Crouau, Y; Bianco, A; Gandois, L; Probst, A

2012-01-01

The toxicity of Pb and Cd+Pb was assessed on the Collembola F. candida in two cultivated soils (SV and AU) with low organic matter (OM) content and circumneutral to basic pH, and an acid forested soil (EPC) with high OM content. Collembola reproduction and growth as well as metal content in Collembola body, in soil, exchangeable fraction and soil solutions, pH and DOC were investigated. Pb and Cd+Pb were the highest in exchangeable fraction and soil solution of the acidic soils. Soil solution pH decreased after metal spiking in every soil due to metal adsorption, which was similar for Cd and the highest in AU for Pb. With increasing Pb and Cd+Pb, the most important reproduction decrease was in EPC soil. The LOEC for reproduction after metal addition was 2400 (Pb) and 200/2400 (Cd/Pb), 1200 and 100/1200, 300 and 100/1200 μg g(-1) for AU, SV and EPC, respectively. The highest and the lowest Pb toxicity was observed for EPC and AU bulk soil, respectively. The metal in Collembola increased with increasing soil concentration, except in AU, but the decreasing BF(solution) with increasing concentrations indicates a limited metal transfer to Collembola or an increased metal removal. Loading high Pb concentrations decreases Cd absorption by the Collembola, but the reverse was not true. The highest Pb toxicity in EPC can be explained by pH and OM content. Because of metal complexation, OM might have a protective role but its ingestion by Collembola lead to higher toxicity. Metal bioavailability in Collembola differs from soil solution indicating that soil solution is not sufficient to evaluate toxicity in soil organisms. The toxicity as a whole decreased when metals were combined, except for Pb in AU, due to adsorption competition between Cd and Pb on clay particles and OM sites in AU and EPC soils, respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

2014-01-01

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

Characterization of upgraded hydrogel biochar from blended rice husk with coal fly ash

NASA Astrophysics Data System (ADS)

Ahmad, Nurul Farhana; Alias, Azil Bahari; Talib, Norhayati; Rashid, Zulkifli Abd; Ghani, Wan Azlina Wan Ab Karim

2017-12-01

Rice husk biochar (RB) blended with coal fly ash (CFA) is used as a material to develop hydrogel for heavy metal removal. This combination, namely hydrogel rice husk biochar-coal fly ash (HRB-CFA) composite is synthesized by embedding the biochar into acrylamide (AAM) as monomer, with N,N'-Methylenebisacrylamide (MBA) as crosslinker and ammonium persulfate (APS) as initiator. While activated carbon (AC) remains an expensive material, HRB-CFA is attracting great interest for its use in the absorption of organic contaminants due to its low material cost and importance as renewable source for securing future energy supply in the environmental system. Although the CFA does not have the surface area as high as AC, certain metallic components that are naturally present in the CFA can play the catalytic role in the removal of heavy metal from wastewater. The percentage of heavy metal removal is depends on the parameters that influence the sorption process; the effect of pH solution, dosage of adsorbent, initial concentration of solution, and contact time. The aim of this study is to characterize HRB-CFA by performing several analyses such as the Brunauer-Emmett-Teller (BET), thermogravimetric (TGA) and field emission scanning electron microscopy (FESEM) methods. The results obtained revealed that the best hydrogel ratio is 0.5:0.5 of blended RB and CFA, as proven by BET surface area, pore volume and pore size of 3.5392 m2/g, 0.00849 cm3/g and 90.566 Å, and the surface morphology showed an increase in porosity size.

Transport and attenuation of metal(loid)s in mine tailings amended with organic carbon: Column experiments

NASA Astrophysics Data System (ADS)

Lindsay, Matthew B. J.; Blowes, David W.; Ptacek, Carol J.; Condon, Peter D.

2011-07-01

A laboratory-scale column experiment was conducted to evaluate the effect of organic carbon amendments on the mobility of As, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Tl and Zn in mine tailings. Three columns were packed with sulfide- and carbonate-rich tailings, which were amended with a 1:1 (vol.) mixture of peat and spent brewing grain at proportions of 0, 2 and 5 vol. %. A simulated input solution characterized by circumneutral pH and elevated concentrations of SO 4 and S 2O 3 was passed through the columns for 540 days. The input solution contained low concentrations of metal(loid)s during the initial 300 days and elevated concentrations thereafter. Decreases in mass transport of S 2O 3 were observed in all columns; with increased attenuation observed at 5 vol. % organic carbon content. Removal of Mn, Ni, Cu, Sb and Mo was observed in all columns during the initial 300 days. However, during this time, mobilization of Fe, As, Zn and Pb was observed, with the greatest increases in concentration observed at the higher organic carbon content. During the final 240 days, S 2O 3 removal was enhanced in columns containing organic carbon, and Fe, Mn, Ni, Tl, As and Sb removal also was observed. This study demonstrates the influence of organic carbon amendments on metal(loid) mobility in mine tailings. Decreases in mass discharge of metal(loid)s may be achieved using this technique; however, site-specific geochemical conditions must be considered before field-scale implementation.

Mobilization of Trace Metals in an Experimental Carbon Sequestration Scenario

NASA Astrophysics Data System (ADS)

Marcon, V.; Kaszuba, J. P.

2012-12-01

Mobilizing trace metals with injection of supercritical CO2 into deep saline aquifers is a concern for geologic carbon sequestration. The potential for leakage from these systems requires an understanding of how injection reservoirs interact with the overlying potable aquifers. Hydrothermal experiments were performed to evaluate metal mobilization and mechanisms of release in a carbonate storage reservoir and at the caprock-reservoir boundary. Experiments react synthetic Desert Creek limestone and/or Gothic Shale, formations in the Paradox Basin, Utah, with brine that is close to equilibrium with these rocks. A reaction temperature of 1600C accelerates the reaction kinetics without changing in-situ water-rock reactions. The experiments were allowed to reach steady state before injecting CO2. Changes in major and trace element water chemistry, dissolved carbon and sulfide, and pH were tracked throughout the experiments. CO2 injection decreases the pH by 1 to 2 units; concomitant mineral dissolution produces elevated Ba, Cu, Fe, Pb, and Zn concentrations in the brine. Concentrations subsequently decrease to approximately steady state values after 120-330 hours, likely due to mineral precipitation as seen in SEM images and predicted by geochemical modeling. In experiments that emulate the caprock-reservoir boundary, final Fe (0.7ppb), an element of secondary concern for the EPA, and Pb (0.05ppb) concentrations exceed EPA limits, whereas Ba (0.140ppb), Cu (48ppb), and Zn (433ppb) values remain below EPA limits. In experiments that simulate deeper reservoir conditions, away from the caprock boundary, final Fe (3.5ppb) and Pb (0.017ppb) values indicate less mobilization than seen at the caprock-reservoir boundary, but values still exceed EPA limits. Barium concentrations always remain below the EPA limit of 2ppb, but are more readily mobilized in experiments replicating deeper reservoir conditions. In both systems, transition elements Cd, Cr, Cu, Pb and Zn behave in a similar manner, increasing in concentration with injection but continually decreasing after about 830 hours until termination of the experiment. SEM images and geochemical models indicate initial dissolution of all rocks and minerals, re-precipitation of Ca-Mg-Fe carbonates and Fe-sulfides, and precipitation of anhydrite in both systems. Calcite dissolves more readily than dolomite in these experiments, but re-precipitates in veins on dolomite. If brines leak from a storage reservoir and mix with a potable aquifer, the experimental results suggest that Ba, Cu, and Zn will not be contaminants of concern. Pb, Fe and As (still under consideration) initially exceed the EPA threshold and may require careful attention in a sequestration scenario. However, experimentally observed trends of decreasing trace metal concentration suggest that these metals could become less of a concern during the life of a carbon repository. Finally, the caprock plays an active role in trace metal mobilization in the system. The caprock provides a source of metals, although subsequent precipitation may remove metals from solution.

Biogenic precipitation of manganese oxides and enrichment of heavy metals at acidic soil pH

NASA Astrophysics Data System (ADS)

Mayanna, Sathish; Peacock, Caroline L.; Schäffner, Franziska; Grawunder, Anja; Merten, Dirk; Kothe, Erika; Büchel, Georg

2014-05-01

The precipitation of biogenic Mn oxides at acidic pH is rarely reported and poorly understood, compared to biogenic Mn oxide precipitation at near neutral conditions. Here we identified and investigated the precipitation of biogenic Mn oxides in acidic soil, and studied their role in the retention of heavy metals, at the former uranium mining site of Ronneburg, Germany. The site is characterized by acidic pH, low carbon content and high heavy metal loads including rare earth elements. Specifically, the Mn oxides were present in layers identified by detailed soil profiling and within these layers pH varied from 4.7 to 5.1, Eh varied from 640 to 660 mV and there were enriched total metal contents for Ba, Ni, Co, Cd and Zn in addition to high Mn levels. Using electron microprobe analysis, synchrotron X-ray diffraction and X-ray absorption spectroscopy, we identified poorly crystalline birnessite (δ-MnO2) as the dominant Mn oxide in the Mn layers, present as coatings covering and cementing quartz grains. With geochemical modelling we found that the environmental conditions at the site were not favourable for chemical oxidation of Mn(II), and thus we performed 16S rDNA sequencing to isolate the bacterial strains present in the Mn layers. Bacterial phyla present in the Mn layers belonged to Firmicutes, Actinobacteria and Proteobacteria, and from these phyla we isolated six strains of Mn(II) oxidizing bacteria and confirmed their ability to oxidise Mn(II) in the laboratory. The biogenic Mn oxide layers act as a sink for metals and the bioavailability of these metals was much lower in the Mn layers than in adjacent layers, reflecting their preferential sorption to the biogenic Mn oxide. In this presentation we will report our findings, concluding that the formation of natural biogenic poorly crystalline birnessite can occur at acidic pH, resulting in the formation of a biogeochemical barrier which, in turn, can control the mobility and bioavailability of heavy metals in acidic soil environments.

Main factors controlling microbial community structure, growth and activity after reclamation of a tailing pond with aided phytostabilization

NASA Astrophysics Data System (ADS)

Zornoza, Raúl; Acosta, José A.; Martínez-Martínez, Silvia; Faz, Ángel; Bååth, Erland

2015-04-01

Reclamation on bare tailing ponds has the potential to represent soil genesis in Technosols favoring the understanding of the changes of microbial communities and function. In this study we used phytostabilization aided with calcium carbonate and pig slurry/manure to reclaim an acidic bare tailing pond with the aim of investigating the effect of amending and different species on microbial community structure and function. We sampled after two years of amending and planting: unamended tailing soil (UTS), non-rhizospheric amended tailing soil (ATS), rhizospheric soil from four species, and non-rhizospheric native forest soil (NS), which acted as reference. The application of amendments increased pH up to neutrality, organic carbon (Corg), C/N and aggregate stability, while decreased salinity and heavy metals availability. No effect of rhizosphere was observed on physicochemical properties, metals immobilization and microbial community structure and function. To account for confounding effects due to soil organic matter, microbial properties were expressed per Corg. The high increments in pH and Corg have been the main factors driving changes in microbial community structure and function. Bacterial biomass was higher in UTS, without significant differences among the rest of soils. Fungal biomass followed the trend UTS < ATS = rhizospheric soils < NS. Bacterial growth increased and fungal growth decreased with increasing pH, despite the high availability of metals at low pH. Enzyme activities were lower in UTS, being β-glucosidase and β-glucosaminidase activities highly correlated with bacterial growth. Microbial activities were not correlated with the exchangeable fraction of heavy metals, indicating that microbial function is not strongly affected by these metals, likely due to the efficiency of the reclamation procedure to reduce metals toxicity. Changes in microbial community composition were largely explained by changes in pH, heavy metals availability and Corg, with increments in fungal and actinobacterial proportions with soil amending. Acknowledgements R. Zornoza acknowledges the financial support to Fundación Séneca-Agencia de Ciencia y Tecnología de la Región de Murcia (Spain).

The stability of amoxicillin trihydrate and potassium clavulanate combination in aqueous solutions.

PubMed

Jerzsele, Akos; Nagy, Gábor

2009-12-01

The effect of various environmental factors on the stability of aqueous solutions of amoxicillin-clavulanic acid combination in a veterinary water-soluble powder product was investigated. In the swine industry, the combination is administered via the drinking water, where both substances are quickly decomposed depending on several environmental factors. The degradation rate of the substances was determined in solutions of different water hardness levels (German hardness of 2, 6 and 10) and pH values (3.0, 7.0 and 10.0), and in troughs made of different materials (metal or plastic). Increasing the water hardness decreased the stability of both substances, amoxicillin being more stable at each hardness value than clavulanate. Amoxicillin trihydrate proved to be most stable at an acidic pH, while increasing the pH decreased its stability (P < 0.05). Maximum stability of potassium clavulanate was experienced at neutral pH, while its decomposition rate was significantly higher at acidic and alkaline pH values (P < 0.01). The stability of the amoxicillin-clavulanic acid combination depends mainly on the less stable clavulanate, although the effect of metallic ions significantly increased the decomposition rate of amoxicillin, rendering it less stable in metal troughs than clavulanate (P < 0.05). Therefore, the amoxicillin-clavulanic acid combination should be administered to the animals in soft water, at neutral pH and in plastic troughs.

Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

DOE PAGES

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan; ...

2016-05-26

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

The surface chemistry of multi-oxide silicates

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

Assessment of heavy metals in loose deposits in drinking water distribution system.

PubMed

Liu, Quanli; Han, Weiqiang; Han, Bingjun; Shu, Min; Shi, Baoyou

2018-06-09

Heavy metal accumulation and potential releases from loose deposits in drinking water distribution system (DWDS) can have critical impacts on drinking water safety, but the associated risks have not been sufficiently evaluated. In this work, the potential biological toxicity of heavy metals in loose deposits was calculated based on consensus-based sediment quality guidelines, and the effects of some of the main water quality parameters, such as the pH and bicarbonate and phosphate content, on the release behaviors of pre-accumulated heavy metals were investigated. The results showed that heavy metals (Cu, As, Cr, Pb, and Cd) significantly accumulated in all the samples, but the contents of the heavy metals were multiple magnitudes lower than the Fe and Mn contents. The potential biotoxicity of As and Cu was relatively high, but the biotoxicity of Cd was negligible. The water quality can significantly influence the release of heavy metals from loose deposits. As the pH increased from 7.0 to 9.0, the release of As and Cr obviously increased. The release of As, Cu, Pb, and Cr also accelerated with the addition of phosphate (from 1 to 5 mg/L). In contrast to the trends for the pH and phosphate, variations in the bicarbonate content did not have a significant influence on the release of As and Cr. The release ratios of heavy metals in the samples were very low, and there was not a correlation between the release rate of the heavy metals in the loose deposits and their potential biotoxicity.

Biosorption of Fe(II) and Mn(II) Ions from Aqueous Solution by Rice Husk Ash

PubMed Central

Zhao, Jiaying; Jiang, Zhao; Shan, Dexin; Lu, Yan

2014-01-01

Rice husk ash (RHA), an agricultural waste, was used as biosorbent for the removal of Iron(II) and Manganese(II) ions from aqueous solutions. The structural and morphological characteristics of RHA and its elemental compositions before and after adsorption of Fe(II) and Mn(II) were determined by scanning electron microscopic (SEM) and X-ray fluorescence (XRF) analyses. Batch experiments were carried out to determine the influence of initial pH, contact time, adsorbent dosage, and initial concentration on the removal of Fe(II) and Mn(II) ions. Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by RHA. The correlation coefficient (R 2) of Langmuir and Freundlich isotherm models equals 0.995 and 0.901 for Fe(II), 0.9862 and 0.8924 for Mn(II), respectively, so the Langmuir model fitted the equilibrium data better than the Freundlich isotherm model. The mean free energy values evaluated from the D-R model indicated that the biosorption of Fe(II) and Mn(II) onto RHA was physical in nature. Experimental data also showed that the biosorption processes of both metal ions complied with the pseudo-second-order kinetics. PMID:24982918

Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption

NASA Astrophysics Data System (ADS)

Padhi, S.; Tokunaga, T.

2017-12-01

Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

Structural and redox properties of mitochondrial cytochrome c co-sorbed with phosphate on hematite (alpha-Fe2O3) surfaces.

PubMed

Khare, Nidhi; Eggleston, Carrick M; Lovelace, David M; Boese, Steven W

2006-11-15

The interaction of metalloproteins with oxides has implications not only for bioanalytical systems and biosensors but also in the areas of biomimetic photovoltaic devices, bioremediation, and bacterial metal reduction. Here, we investigate mitochondrial ferricytochrome c (Cyt c) co-sorption with 0.01 and 0.1 M phosphate on hematite (alpha-Fe2O3) surfaces as a function of pH (2-11). Although Cyt c sorption to hematite in the presence of phosphate is consistent with electrostatic attraction, other forces act upon Cyt c as well. The occurrence of multilayer adsorption, and our AFM observations, suggest that Cyt c aggregates as the pH approaches the Cyt c isoelectric point. In solution, methionine coordination of heme Fe occurs only between pH 3 and 7, but in the presence of phosphate this coordination is retained up to pH 10. Electrochemical evidence for the presence of native Cyt c occurs down to pH 3 and up to pH 10 in the absence of phosphate, and this range is extended to pH 2 and 11 in the presence of phosphate. Cyt c that initially adsorbs to a hematite surface may undergo conformation change and coat the surface with unfolded protein such that subsequently adsorbing protein is more likely to retain the native conformational state. AFM provides evidence for rapid sorption kinetics for Cyt c co-sorbed with 0.01 or 0.1 M phosphate. Cyt c co-sorbed with 0.01 M phosphate appears to unfold on the surface of hematite while Cyt c co-sorbed with 0.1 M phosphate possibly retains native conformation due to aggregation.

Biosorption of copper by cyanobacterial bloom-derived biomass harvested from the eutrophic Lake Dianchi in China.

PubMed

Wang, Kan; Colica, Giovanni; De Philippis, Roberto; Liu, Yongding; Li, Dunhai

2010-10-01

Biomass of cyanobacterial bloom from Lake Dianchi was used as a biosorbent for copper removal from aqueous solution. The maximum capacity was found at conditions of pH 4, initial concentration of copper was 10 mg/l and initial dose of biomass was 1.0 g/l. HNO(3) demonstrated the highest desorption efficiency compared with HCl, EDTA, and citric acid. Physical adsorption was assumed not to be the dominant mechanism of biosorption as revealed by scanning electron microscopy and surface area measurement of the biomass. Infrared ray spectra analysis of the biomass suggested that ion-exchange is the principal mechanism for biosorption. Considering the advantages-low cost, easy to collect, and huge in quantity-the Microcystis bloom biomass could be used as a sorbent for copper and other heavy metals removal.

Gold Binding by Native and Chemically Modified Hops Biomasses

PubMed Central

López, M. Laura; Peralta-Videa, J. R.; de la Rosa, G.; Armendáriz, V.; Herrera, I.; Troiani, H.; Henning, J.

2005-01-01

Heavy metals from mining, smelting operations and other industrial processing facilities pollute wastewaters worldwide. Extraction of metals from industrial effluents has been widely studied due to the economic advantages and the relative ease of technical implementation. Consequently, the search for new and improved methodologies for the recovery of gold has increased. In this particular research, the use of cone hops biomass (Humulus lupulus) was investigated as a new option for gold recovery. The results showed that the gold binding to native hops biomass was pH dependent from pH 2 to pH 6, with a maximum percentage binding at pH 3. Time dependency studies demonstrated that Au(III) binding to native and modified cone hops biomasses was found to be time independent at pH 2 while at pH 5, it was time dependent. Capacity experiments demonstrated that at pH 2, esterified hops biomass bound 33.4 mg Au/g of biomass, while native and hydrolyzed hops biomasses bound 28.2 and 12.0 mg Au/g of biomass, respectively. However, at pH 5 the binding capacities were 38.9, 37.8 and 11.4 mg of Au per gram of native, esterified and hydrolyzed hops biomasses, respectively. PMID:18365087

Interactions of flavonoids with iron and copper ions: a mechanism for their antioxidant activity.

PubMed

Mira, Lurdes; Fernandez, M Tereza; Santos, Marta; Rocha, Rui; Florêncio, M Helena; Jennings, Keith R

2002-11-01

The metal chelating properties of flavonoids suggest that they may play a role in metal-overload diseases and in all oxidative stress conditions involving a transition metal ion. A detailed study has been made of the ability of flavonoids to chelate iron (including Fe3+) and copper ions and its dependence of structure and pH. The acid medium may be important in some pathological conditions. In addition, the ability of flavonoids to reduce iron and copper ions and their activity-structure relationships were also investigated. To fulfill these objectives, flavones (apigenin, luteolin, kaempferol, quercetin, myricetin and rutin), isoflavones (daidzein and genistein), flavanones (taxifolin, naringenin and naringin) and a flavanol (catechin) were investigated. All flavonoids studied show higher reducing capacity for copper ions than for iron ions. The flavonoids with better Fe3+ reducing activity are those with a 2,3-double bond and possessing both the catechol group in the B-ring and the 3-hydroxyl group. The copper reducing activity seems to depend largely on the number of hydroxyl groups. The chelation studies were carried out by means of ultraviolet spectroscopy and electrospray ionisation mass spectrometry. Only flavones and the flavanol catechin interact with metal ions. At pH 7.4 and pH 5.5 all flavones studied appear to chelate Cu2+ at the same site, probably between the 5-hydroxyl and the 4-oxo groups. Myricetin and quercetin, however, at pH 7.4, appear to chelate Cu2+ additionally at the ortho-catechol group, the chelating site for catechin with Cu2+ at pH 7.4. Chelation studies of Fe3+ to flavonoids were investigated only at pH 5.5. Only myricetin and quercetin interact strongly with Fe3+, complexation probably occurring again between the 5-hydroxyl and the 4-oxo groups. Their behaviour can be explained by their ability to reduce Fe3+ at pH 5.5, suggesting that flavonoids reduce Fe3+ to Fe2+ before association.

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture.

PubMed

Zhi-xin, Niu; Sun, Li-na; Sun, Tie-heng; Li, Yu-shuang; Wang, Hong

2007-01-01

Soil contaminated with heavy metals cadmium (Cd) and lead (Pb) is hard to be remediated. Phytoremediation may be a feasible method to remove toxic metals from soil, but there are few suitable plants which can hyperaccumulate metals. In this study, Cd and Pb accumulation by four plants including sunflower (Helianthus annuus L.), mustard (Brassica juncea L.), alfalfa (Medicago sativa L.), ricinus (Ricinus communis L.) in hydroponic cultures was compared. Results showed that these plants could phytoextract heavy metals, the ability of accumulation differed with species, concentrations and categories of heavy metals. Values of BCF (bioconcentration factor) and TF (translocation factor) indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals. Changes on the biomass of plants, pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures. Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals, such as pH and Eh regulations, and so forth.

Nuclear reactor cooling system decontamination reagent regeneration. [PWR; BWR

DOEpatents

Anstine, L.D.; James, D.B.; Melaika, E.A.; Peterson, J.P. Jr.

1980-06-06

An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution is described. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.

Metal release from stainless steel particles in vitro-influence of particle size.

PubMed

Midander, K; Pan, J; Wallinder, I Odnevall; Leygraf, C

2007-01-01

Human inhalation of airborne metallic particles is important for health risk assessment. To study interactions between metallic particles and the human body, metal release measurements of stainless steel powder particles were performed in two synthetic biological media simulating lung-like environments. Particle size and media strongly influence the metal release process. The release rate of Fe is enhanced compared with Cr and Ni. In artificial lysosomal fluid (ALF, pH 4.5), the accumulated amounts of released metal per particle loading increase drastically with decreasing particle size. The release rate of Fe per unit surface area increases with decreasing particle size. Compared with massive sheet metal, fine powder particles (<4 microm) show similar release rates of Cr and Ni, but a higher release rate of Fe. Release rates in Gamble's solution (pH 7.4), for all powders investigated, are significantly lower compared to ALF. No clear trend is seen related to particle size in Gamble's solution.

Nuclear reactor cooling system decontamination reagent regeneration

DOEpatents

Anstine, Larry D.; James, Dean B.; Melaika, Edward A.; Peterson, Jr., John P.

1985-01-01

An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.

Questa baseline and pre-mining ground-water quality investigation. 19. Leaching characteristics of composited materials from mine waste-rock piles and naturally altered areas near Questa, New Mexico

USGS Publications Warehouse

Smith, Kathleen S.; Hageman, Philip L.; Briggs, Paul H.; Sutley, Stephen J.; McCleskey, R. Blaine; Livo, K. Eric; Verplanck, Philip L.; Adams, Monique G.; Gemery-Hill, Pamela A.

2007-01-01

The goal of this study is to compare and contrast the leachability of metals and the acidity from individual mine waste-rock piles and natural erosional scars in the study area near Questa, New Mexico. Surficial multi-increment (composite) samples less than 2 millimeters in diameter from five waste-rock piles, nine erosional-scar areas, a less-altered site, and a tailings slurry-pipe sample were analyzed for bulk chemistry and mineralogy and subjected to two back-to-back leaching procedures. The first leaching procedure, the U.S. Geological Survey Field Leach Test (FLT), is a short-duration leach (5-minute shaking and 10-minute settling) and is intended to leach readily soluble materials. The FLT was immediately followed by an 18-hour, end-over-end rotation leaching procedure. Comparison of results from the back-to-back leaching procedures can provide information about reactions that may take place upon migration of leachates through changing geochemical conditions (for example, pH changes), both within the waste-rock and scar materials and away from the source materials. For the scar leachates, the concentrations of leachable metals varied substantially between the scar areas sampled. The scar leachates have low pH (pH 3.2-4.1). Under these low-pH conditions, cationic metals are solubilized and mobile, but anionic species, such as molybdenum, are less soluble and less mobile. Generally, metal concentrations in the waste-rock leachates did not exceed the upper range of those metal concentrations in the erosional-scar leachates. One exception is molybdenum, which is notably higher in the waste-rock leachates compared with the scar leachates. Most of the waste-rock leachates were at least mildly acidic (pH 3.0-6.2). The pH values in the waste-rock leachates span a large pH range that includes some pH-dependent solubility and metal-attenuation reactions. An increase in pH with leaching time and agitation indicates that there is pH-buffering capacity in some of the waste-rock piles. As pH increased in the waste-pile leachates, concentrations of several metals decreased with increasing time and agitation. Similar pH-dependent reactions may take place upon migration of the leachates in the waste-rock piles. Bulk chemistry, mineralogy, and leachate sulfur-isotope data indicate that the Capulin and Sugar Shack West waste-rock piles are compositionally different from the younger Sugar Shack South, Sugar Shack Middle, and Old Sulphur Gulch piles. The Capulin and Sugar Shack West piles have the lowest-pH leachates (pH 3.0-4.1) of the waste-pile samples, and the source material for the Capulin and Sugar Shack West piles appears to be similar to the source material for the erosional-scar areas. Calcite dissolution, in addition to gypsum dissolution, appears to produce the calcium and sulfate concentrations in leachates from the Sugar Shack South, Sugar Shack Middle, and Old Sulphur Gulch piles.

Microstructures, mechanical properties, and fracture behaviors of metal-injection molded 17-4PH stainless steel

NASA Astrophysics Data System (ADS)

Wu, Ming-Wei; Huang, Zeng-Kai; Tseng, Chun-Feng; Hwang, Kuen-Shyang

2015-05-01

Metal injection molding (MIM) is a versatile technique for economically manufacturing various metal parts with complicated shapes and excellent properties. The objective of this study was to clarify the effects of powder type (water-atomized and gas-atomized powders) and various heat treatments (sintering, solutioning, H900, and H1100) on the microstructures, mechanical properties, and fracture behaviors of MIM 17-4PH stainless steels. The results showed that better mechanical properties of MIM 17-4PH can be achieved with gas-atomized powder than with water-atomized powder due mainly to the lower silicon and oxygen contents and fewer SiO2 inclusions in the steels. The presence of 10 vol% δ ferrite does not impair the UTS or elongation of MIM 17-4PH stainless steels. The δ ferrite did not fracture, even though the neighboring martensitic matrix was severely cracked. Moreover, H900 treatment produces the highest hardness and UTS, along with moderate elongation. H1100 treatment produces the best elongation, along with moderate hardness and UTS.

The effect of solution pH on the electrochemical performance of nanocrystalline metal ferrites MFe2O4 (M=Cu, Zn, and Ni) thin films

NASA Astrophysics Data System (ADS)

Elsayed, E. M.; Rashad, M. M.; Khalil, H. F. Y.; Ibrahim, I. A.; Hussein, M. R.; El-Sabbah, M. M. B.

2016-04-01

Nanocrystalline metal ferrite MFe2O4 (M=Cu, Zn, and Ni) thin films have been synthesized via electrodeposition-anodization process. Electrodeposited (M)Fe2 alloys were obtained from aqueous sulfate bath. The formed alloys were electrochemically oxidized (anodized) in aqueous (1 M KOH) solution, at room temperature, to the corresponding hydroxides. The parameters controlling the current efficiency of the electrodeposition of (M)Fe2 alloys such as the bath composition and the current density were studied and optimized. The anodized (M)Fe2 alloy films were annealed in air at 400 °C for 2 h. The results revealed the formation of three ferrite thin films were formed. The crystallite sizes of the produced films were in the range between 45 and 60 nm. The microstructure of the formed film was ferrite type dependent. The corrosion behavior of ferrite thin films in different pH solutions was investigated using open circuit potential (OCP) and potentiodynamic polarization measurements. The open circuit potential indicates that the initial potential E im of ZnFe2O4 thin films remained constant for a short time, then sharply increased in the less negative direction in acidic and alkaline medium compared with Ni and Cu ferrite films. The values of the corrosion current density I corr were higher for the ZnFe2O4 films at pH values of 1 and 12 compared with that of NiFe2O4 and CuFe2O4 which were higher only at pH value 1. The corrosion rate was very low for the three ferrite films when immersion in the neutral medium. The surface morphology recommended that Ni and Cu ferrite films were safely used in neutral and alkaline medium, whereas Zn ferrite film was only used in neutral atmospheres.

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

PubMed

Yin, Jun; Hu, Ying; Yoon, Juyoung

2015-07-21

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

The rapid growth of 3 µm long titania nanotubes by anodization of titanium in a neutral electrochemical bath

NASA Astrophysics Data System (ADS)

Lockman, Zainovia; Ismail, Syahriza; Sreekantan, Srimala; Schmidt-Mende, L.; MacManus-Driscoll, J. L.

2010-02-01

The length of titania nanotubes formed by anodization of 0.1 mm thick titanium foil was found to be a strong function of the pH of the electrolyte. The longest nanotubes were formed by using an electrolyte consisting of 1 M Na2SO4 plus 5 wt% NH4F with pH 7. At this pH, after 30 min of anodization, 3 µm length nanotubular titania arrays with top diameters of ~50 nm and bottom diameters of 100 nm were produced. No acid was added to this electrolyte. The formation of titania nanotubes in neutral pH systems was therefore successful due to the excess NH4F in the electrolyte which increases the chemical dissolution process at the metal/oxide interface. Since the pH of the electrolyte at the top part of the nanotubes is kept very high, the dissolution of the nanotubes at the surface is minimal. However, the amount is adequate to remove the initial barrier layer, forming a rather well-defined nanoporous structure. All anodized foils were weakly crystalline and the transformation to anatase phase was achieved by heat treatment at temperatures from 200 to 500 °C for 1 h in air. Annealing at temperatures above 500 °C induce rutile phase formation and annealing at higher temperatures accelerates the diffusion of Ti4+ leading to excessive growth and the nanotubular structure diminishes.

Matrix elimination method for the determination of precious metals in ores using electrothermal atomic absorption spectrometry.

PubMed

Salih, Bekir; Celikbiçak, Omür; Döker, Serhat; Doğan, Mehmet

2007-03-28

Poly(N-(hydroxymethyl)methacrylamide)-1-allyl-2-thiourea) hydrogels, poly(NHMMA-ATU), were synthesized by gamma radiation using (60)Co gamma source in the ternary mixture of NHMMA-ATU-H(2)O. These hydrogels were used for the specific gold, silver, platinum and palladium recovery, pre-concentration and matrix elimination from the solutions containing trace amounts of precious metal ions. Elimination of inorganic matrices such as different transition and heavy metal ions, and anions was performed by adjusting the solution pH to 0.5 that was the selective adsorption pH of the precious metal ions. Desorption of the precious metal ions was performed by using 0.8 M thiourea in 3M HCl as the most efficient desorbing agent with recovery values more than 95%. In the desorption medium, thiourea effect on the atomic signal was eliminated by selecting proper pyrolysis and atomization temperatures for all precious metal ions. Precision and the accuracy of the results were improved in the graphite furnace-atomic absorption spectrometer (GFAAS) measurements by applying the developed matrix elimination method performing the adsorption at pH 0.5. Pre-concentration factors of the studied precious metal ions were found to be at least 1000-fold. Detection limits of the precious metal ions were found to be less than 10 ng L(-1) of the all studied precious metal ions by using the proposed pre-concentration method. Determination of trace levels of the precious metals in the sea-water, anode slime, geological samples and photographic fixer solutions were performed using GFAAS clearly after applying the adsorption-desorption cycle onto the poly(NHMMA-UTU) hydrogels.

Metal Oxides and Ion-Exchanging Surfaces as pH Sensors in Liquids: State-of-the-Art and Outlook

PubMed Central

Kurzweil, Peter

2009-01-01

Novel applications of online pH determinations at temperatures from -35 °C to 130 °C in technical and biological media, which are all but ideal aqueous solutions, require new approaches to pH monitoring. The glass electrode, introduced nearly hundred years ago, and chemical sensors based on field effect transistors (ISFET) show specific drawbacks with respect to handling and long-time stability. Proton sensitive metal oxides seem to be a promising and alternative to the state-of-the-art measuring methods, and might overcome some problems of classical hydrogen electrodes and reference electrodes. PMID:22408563

The Cytosolic pH of Individual Saccharomyces cerevisiae Cells Is a Key Factor in Acetic Acid Tolerance.

PubMed

Fernández-Niño, Miguel; Marquina, Maribel; Swinnen, Steve; Rodríguez-Porrata, Boris; Nevoigt, Elke; Ariño, Joaquín

2015-11-01

It was shown recently that individual cells of an isogenic Saccharomyces cerevisiae population show variability in acetic acid tolerance, and this variability affects the quantitative manifestation of the trait at the population level. In the current study, we investigated whether cell-to-cell variability in acetic acid tolerance could be explained by the observed differences in the cytosolic pHs of individual cells immediately before exposure to the acid. Results obtained with cells of the strain CEN.PK113-7D in synthetic medium containing 96 mM acetic acid (pH 4.5) showed a direct correlation between the initial cytosolic pH and the cytosolic pH drop after exposure to the acid. Moreover, only cells with a low initial cytosolic pH, which experienced a less severe drop in cytosolic pH, were able to proliferate. A similar correlation between initial cytosolic pH and cytosolic pH drop was also observed in the more acid-tolerant strain MUCL 11987-9. Interestingly, a fraction of cells in the MUCL 11987-9 population showed initial cytosolic pH values below the minimal cytosolic pH detected in cells of the strain CEN.PK113-7D; consequently, these cells experienced less severe drops in cytosolic pH. Although this might explain in part the difference between the two strains with regard to the number of cells that resumed proliferation, it was observed that all cells from strain MUCL 11987-9 were able to proliferate, independently of their initial cytosolic pH. Therefore, other factors must also be involved in the greater ability of MUCL 11987-9 cells to endure strong drops in cytosolic pH. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

The Cytosolic pH of Individual Saccharomyces cerevisiae Cells Is a Key Factor in Acetic Acid Tolerance

PubMed Central

Fernández-Niño, Miguel; Marquina, Maribel; Swinnen, Steve; Rodríguez-Porrata, Boris

2015-01-01

It was shown recently that individual cells of an isogenic Saccharomyces cerevisiae population show variability in acetic acid tolerance, and this variability affects the quantitative manifestation of the trait at the population level. In the current study, we investigated whether cell-to-cell variability in acetic acid tolerance could be explained by the observed differences in the cytosolic pHs of individual cells immediately before exposure to the acid. Results obtained with cells of the strain CEN.PK113-7D in synthetic medium containing 96 mM acetic acid (pH 4.5) showed a direct correlation between the initial cytosolic pH and the cytosolic pH drop after exposure to the acid. Moreover, only cells with a low initial cytosolic pH, which experienced a less severe drop in cytosolic pH, were able to proliferate. A similar correlation between initial cytosolic pH and cytosolic pH drop was also observed in the more acid-tolerant strain MUCL 11987-9. Interestingly, a fraction of cells in the MUCL 11987-9 population showed initial cytosolic pH values below the minimal cytosolic pH detected in cells of the strain CEN.PK113-7D; consequently, these cells experienced less severe drops in cytosolic pH. Although this might explain in part the difference between the two strains with regard to the number of cells that resumed proliferation, it was observed that all cells from strain MUCL 11987-9 were able to proliferate, independently of their initial cytosolic pH. Therefore, other factors must also be involved in the greater ability of MUCL 11987-9 cells to endure strong drops in cytosolic pH. PMID:26341199

Ultrasonically assisted solvothermal synthesis of novel Ni/Al layered double hydroxide for capturing of Cd(II) from contaminated water

NASA Astrophysics Data System (ADS)

Rahmanian, Omid; Maleki, Mohammad Hassan; Dinari, Mohammad

2017-11-01

A novel adsorbent of nickel aluminum layered double hydroxide (Ni/Al-LDH) was prepared through the precipitation of metal nitrates by ultrasonically assisted solvothermal method. The surface morphology, chemical structure and thermal properties of this compound were examined by X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) techniques. The XRD, TEM and FE-SEM results established that the synthesized LDH have a well-ordered layer structure with good crystalline nature. Then it was applied to remove excessive Cd(II) ions from water and the effects of contact time, pH and adsorbent dose were examined at initial Cd(II) concentration of 10 mg/L. Results show that the time required to reach equilibrium was fast (40 min) and working pH solution was neutral (pH 7). Langmuir and Freundlich model of adsorption isotherms were explored; the results show that the Freundlich model was better fitted than that Langmuir model. This results predicting a multilayer adsorption of Cd(II) on LDH. The equilibrium kinetic adsorption data were fixed to the pseudo-second order kinetic equation.

Cylindrical Electrolyser Enhanced Electrokinetic Remediation of Municipal Solid Waste Incineration Fly Ashes

NASA Astrophysics Data System (ADS)

Huang, Tao; Zhou, Lulu; Tao, Junjun; Liu, Longfei

2018-01-01

The paper discusses enhancement and efficiency of removing spiked heavy metal (HM) contaminants from the municipal solid waste incineration (MSWI) fly ashes in the cylindrical electrolyser device. The characterization parameters of the electrolyte solution pH, electric current, electrical conductivity, voltage gradient were discussed after the experiment. The chemical speciation of HMs was analysed between the original samples and remediated ones by BCR sequential extraction. The detoxification efficiencies of Zn, Pb, Cu and Cd in the column-uniform device were compared with that in the traditional rectangular apparatus. The pH value changed smoothly with small amplitude of oscillation in general in cathode and anode compartments except the initial break. The electrical current rapidly increased on the first day of the experiment and steadily declined after that and the electrical conductivity presented a clear rising trend. The residual partition of detoxified samples were obviously lifted which was much higher than the analysis data of the raw materials. The pH and the electrical conductivity in sample region were distributed more uniformly and the blind area was effectively eliminated in the electrolytic cells which was indirectly validated by the contrastive detoxification result of the spiked HMs between the rectangular and cylindrical devices.