Water-soluble polymermetal ion interactions. Engineering metal (hydr)oxide sorbents for removal of arsenate and similar weak-acid oxyanion contaminants: a critical review with emphasis on factors governing sorption processes. doi: 10.1016/j.reactfunctpolym.2012.06.008, Urbano, B. F., Villenas, I., Rivas, B. L., and Campos, C. H. (2015). doi: 10.1065/jss2005.01.126, Grover, V. A., Hu, J., Engates, K. E., and Shipley, H. J. Sci. The scientific community is interested to find new methods to produce water of quality, using technologies of low cost, easy use, and higher efficiency compared to conventional treatment such as coagulation and flocculation, chemical precipitation, electrochemical treatment, adsorption, and ion-exchange (Asman, 2009; Chen et al., 2009; Doula, 2009; Nanseu-Njiki et al., 2009; Duan et al., 2010; Jiang et al., 2010). The R(%) of arsenic showed that the best performances are found at 10 and 20 wt-% tin content for both arsenic species with a maximum retention at pH 8 and 4 (Rivas and Aguirre, 2007). Mater. Sci. B 114, 67796785. However, the copolymer showed a marked selectivity toward nickel ions and the retention of Cu2+ and Cd(II) increased respect to PVP. Tan, P., Sun, J., Hu, Y., Fang, Z., Bi, Q., Chen, Y., et al. 89, 249258. The authors thank to FONDECYT (Grant No 1150510). However, considering the arsenic speciation, majority remains as As(III) with traces of As(V), less than 10 wt-% in the filtrate solution (Rivas and Aguirre, 2007). This is probably due to the interaction of the carboxylate groups of the P(AA) with the quaternary ammonium groups of P(ClMPTA) (Rivas et al., 2006). Bio-nanocomposites for food packaging applications. Sep. Sci. Firstly, we envision that the future research trends in the field of composite adsorbent compounds should focus on the obtaining of materials with a high specific surface to give a high contact area between the adsorbent and the contaminant. Hybrid materials where the organic and inorganic phase are intimately mixed can be obtained for metal ion depollution. Similarly, the obtaining of a hybrid composite, where the polymer chains and the oxide network oxide are mixed at the molecular level, are novel materials to be used in adsorption processes. Coating carbon nanotubes with humic acid using an eco-friendly mechanochemical method: application for Cu(II) ions removal from water and aquatic ecotoxicity. Selective removal of the heavy metal ions from waters and industrial wastewaters by ion-exchange method. This effect is higher when the ratio polycation:polyanion > 1, where a considerable portion of ammonium groups are free to interact and remove arsenate anions (see Figure 3). 492, 176190. Chem. doi: 10.1007/s00289-012-0785-z, Rivas, B. L., Pereira, E. D., and Moreno-Villoslada, I. Eur. In addition, different polymer:As(V) molar ratios (31:1, 20:1, 10:1, 6:1, and 3:1) have been studied. Hazard. The LPR technique with poly(2-acrylamido-2-methylpropanesulfonate sodium) (PAMPS) as sorbent was used for the removal of heavy metal ions from water. 31, 298305. A partial oxidation of As(III) to As(V) is probably due to the higher tin content in the polymer. When the copolymer prepared at molar ratio of 1:1 was used in LPR, the copolymer loses its ability to bind the As(V) independent of the pH. Chain characteristics of poly (2-acrylamido-2-methylpropanesulfonate) polymers. Res. A 2, 1941519426.
Res. Chemosphere 171, 126133. Adsorption of Cu2+, Cd2+ and Ni2+ from aqueous single metal solutions on graphene oxide membranes. The sulfonic acid polymers PAMPS [poly (2-acrylamido-2-methyl-1-propanesulfonic acid)] and related analogues are highly potent inhibitors of angiogenesis. Technol. Sci. doi: 10.1016/j.jcis.2008.11.068, Jiang, M.-Q., Jin, X.-Y., Lu, X.-Q., and Chen, Z.-L. (2010). (2011). Lead (Pb2+) and copper (Cu2+) remediation from water using superparamagnetic maghemite (-Fe2O3) nanoparticles synthesized by Flame Spray Pyrolysis (FSP). J. Polym. J. (2013). In this case, the structures of the polymers can be homopolymer or copolymers, and variables such as pH and concentration not only influence the interaction with metal ions but also the polymer chains conformation in solution. Figure 3. The removal of arsenic by water-soluble polymer was obtained in a 99% yield using a 20:1 polymer:As(V) molar ratio at a pH value of 9. Polymer nanocomposites that combine the different properties of inorganic compounds and polymers, can not only enhance the physical properties (for example, mechanical stability), but also, the addition of nanoparticles can provide novel functionalities such ads magnetic characteristics useful to facilitated the separation, or new surfaces of interaction that improve the efficiency and selectivity of the adsorption. Modeling the sorption kinetics of divalent metal ions to hematite. doi: 10.1016/j.watres.2009.03.007, Chou, Y.-H., Choo, K.-H., Chen, S.-S., Yu, J.-H., Peng, C.-Y., and Li, C.-W. (2018). Chem. The LPR technique was also used in the removal of Cr(VI) ions from aqueous solution using water-soluble poly(diallyldimethylammonium chloride), PDDA, and subsequent electrochemical reduction of Cr(VI) to Cr(III) (Snchez et al., 2017). Eng. Arsenic sorption onto an aluminum oxyhydroxide-poly[(4-vinylbenzyl)trimethylammonium chloride] hybrid sorbent. (2013). (2012). J. Colloid Interface Sci. The hybrid exhibited the capability to retain arsenite and arsenate directly, and the sorption to various arsenic species was modulated by changing the inorganic-polymeric composition in the material. Water Res. Sci. Eng. doi: 10.1016/j.cej.2014.02.093, Pan, B., Xu, J., Wu, B., Li, Z., and Liu, X. 72, 642649. Arsenate removal by nanostructured ZrO2 spheres. doi: 10.1080/01496390902729148, Bandaru, N. M., Reta, N., Dalal, H., Ellis, A. V., Shapter, J., and Voelcker, N. H. (2013). 
Environ. Eng. Likewise, the sorption of Cu(II) was carried out with novel hybrid adsorbentscontaining thiol groups. Precipitation of heavy metals from wastewater using simulated flue gas: sequent additions of fly ash, lime and carbon dioxide. Many applications of water-soluble polymers for the selective separation or concentration of various metal ions from water, have been reported in the literature. On the other hand, the retention capacity of copolymer was lower compared to PAMPS. doi: 10.1002/ep.11876, Asman, G. (2009). Res. 6:320. doi: 10.3389/fchem.2018.00320. The (%R) of PAMPS was similar at both pH values (3.2 and 5.7), which indicates that the protons of the media are not interfering on the metal removal. J. Understanding arsenate reaction kinetics with ferric hydroxides. PVP does not contain ionizable groups and this allows a major folding of the macromolecular chains, which diminished the access of metal ions to PVP compared to PAMPS.
A new hybrid (polymer/inorganic) fibrous sorbent for arsenic removal from drinking water. 46, 41114120. 361, 509520. 261, 534541. 38, 24992504. J. Prog. doi: 10.1016/j.jhazmat.2015.04.068, Thakur, S. S., and Chauhan, G. S. (2014). Adsorption of Pb (II), Cd (II), Ni (II) and Cu (II) onto natural kaolinite clay. Eng. Chem. Characteristics of equilibrium, kinetics studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic chitosan microspheres. The experimental results indicated the retention of Ni(II) was achieved selectively compared to null retention of Cu(II) and Cd(II) at both pH values using PVP at pH 3.2 and 5.7. The pH of the media can influence the conformation of the polymer. 43, 16911698. 
(2009). Adsorption of Cu(II), Co(II), and Ni(II) ions by modified magnetic chitosan chelating resin. Chem. 8, 16671681. ACS Appl. Eng. Environ. (2017). Heavy metal removal from water/wastewater by nanosized metal oxides: a review. doi: 10.1002/pi.3178, Urbano, B., Rivas, B. L., Martinez, F., and Alexandratos, S. D. (2012a).
Based on the literature, a pendant-type polycation can form an equimolar complex with the polyanion. The ultrafiltration membrane is the most suitable filter for LPR studies, and a huge amount of data has being reported (Snchez and Rivas, 2011). doi: 10.1016/S0043-1354(02)00238-5, Dong, Q., Liu, J., Song, L., and Shao, G. (2011). Int. Mater. (2012). In one study, the chemical reduction was proposed to recover copper from the retentate obtained by LPR technique. However, Pb(II) and Cr(III) have more stable electronic structures, preventing complex formation (Rivas et al., 2012). Sci. Mater. Interestingly, the order of affinity among the metal ions follows the same order corresponding to the stability constants between the lanthanide ions and non-immobilized DTPA (Roosen et al., 2014). 170, 381394. J. Appl. In this sense, the development of highly selective adsorbents, novel architectures, high stability, or materials with a significant improvement in the performance compared to existing adsorbents, can find a niche for their development and eventually reach their marketing. Water Res. Polym. 131, 40871. doi: 10.1002/APP.40871. (2012). Ion-exchange resins: a retrospective from industrial and engineering chemistry research. Novel zwitterionic inorganicorganic hybrids: synthesis of hybrid adsorbents and their applications for Cu2+ removal.
Selectivity studies were carried out to pH 4, 6, and 8 using polymer:As (20:1), (100:1), (200:1), (400:1) and (600:1) molar ratio. doi: 10.1021/es400919t, Zhang, Y., and Li, Z. Plasma-induced grafting of cyclodextrin onto multiwall carbon nanotube/iron oxides for adsorbent application. 109, 327336. doi: 10.1016/j.desal.2009.11.005, Kagz, H., Durmu, A., and Kagz, A.
J. 1. Despite these good results, the selectivity of the technique can be improved. B Solid State Mater. In general, P(ClVBTA) and P(ClAETA) showed higher retention capacities to As(V) species at pH values 8 and 6 compared to 4. In this context our objective was to obtain water-soluble polymers, such as non-cationic system, that is manifested thorough a complex reaction of metallic active site with toxic species to recuperate. Efficient removal of Cr(VI) by polyelectrolyte-assisted ultrafiltration and subsequent electrochemical reduction to Cr(III). (2010). At pH 4.8, PAA chains can be contracted and metal ions can be complexed with 2-4 carboxylic acid groups (Rivas and Aguirre, 2007). The results showed that by using P(GMA-NMG) as supporting electrolyte during the complete EO of As(III) to As(V) followed by LPR separation, almost 80% of As(V) was removed at pH 10 (Arar et al., 2014). 80, 436441. (2006), Rivas and Aguirre (2007). Jeon, B. H., Dempsey, B.
The filtration factor is defined as the ratio of the filtrate volume (Vf) to the cell volume (Vo) (Snchez and Rivas, 2011). The experiments were carried out with (20:1), (100:1), (200:1), (400:1), and (600:1) poly(AA)-Sn:As(III) mol ratios at pH 8. 64, 805813. 99, 255264. 41, 24342442. Eng. Although, some composite adsorbents compounds have reached their marketing successfully (Lewatit, Ferrix), in general, the complexities of these composite systems increase the costs by making them less attractive to its arrival on the market. A 546, 9198. doi: 10.1016/j.jcis.2010.08.023, Kotal, M., and Bhowmick, A. K. (2015). (2006), Rivas and Aguirre (2007). (2009). Water Res. Sn(II) could coordinate as 2-4 carboxylate groups in structure conventionally bidentate but they are not symmetric. doi: 10.1016/j.gexplo.2014.10.005, Ahmed, M. A., Ali, S. M., El-Dek, S. I., and Galal, A. 101, 230240. Technol. Environ. Energy 33, 918924. Prog. doi: 10.1016/j.jcis.2011.05.031, Pavlidou, S., and Papaspyrides, C. D. (2008).
Prog. It is known that polyamines such as poly(ethyleneimine) P(EI) are suitable macromolecular ligands for the complexation-ultrafiltration of metal ions. J. Colloids Surf. Sustain. On the other hand, the capture of arsenic from aqueous media is important by high toxicity and environmental impact (Snchez et al., 2015). J. Polym. Effect of the polymer: As(V) molar ratio on the retention of As(V) for the two polymers at a pH of 8 and filtration factor of Z = 10. 281, 826836. 132, 41272. doi: 10.1002/app.41272, Vatutsina, O. M., Soldatov, V. S., Sokolova, V. I., Johann, J., Bissen, M., and Weissenbacher, A. The bands at 777 and 540 cm1 confirmed the Sn-O bond (Rivas and Aguirre, 2007). At basic pH the divalent HAsO42- species predominate in solution and can be retained easily by polymers (Snchez and Rivas, 2011). (2007). The arsenite retention by P(AA) is negligible, independent of the pH. 43, 36593672. Sci. Three different polymers (PSS, PAA, and PEI) were studied to explore their effects on the copper removal in LPR and on the copper recovery by chemical reduction under various pH conditions (Chou et al., 2018). It is observed that when the amount of quaternary ammonium groups increases in the copolymers (4:1), an enhanced retention of arsenic is reached, similar to that of pure P(ClMPTA). 36, 294322. 31, 360372. Eng. A great advantage of the LPR is the retention of inorganic species in a homogenous medium, avoiding in great part the mass transfer phenomena or diffusion phenomena that are present in a heterogeneous system. Effects of crystal modification on the binding of trace metals and arsenate by goethite. Eng. A. Polym. (2010). (2005). (2011). (2006). soluble insoluble substances materials science kindergarten montessoriprintshop montessori 
Tech. Ind. Polymerzirconium oxide nanoparticles have been successfully applied in the sorption of As(V), As(III), Cr(VI), and fluoride (Kosmulski, 2002; Mandal et al., 2013; Pan et al., 2013, 2014; Padungthon et al., 2014; Hua et al., 2017). Water-soluble polymers containing quaternary ammonium groups have been studied in combination with ultrafiltration membranes as arsenic sorbents. In addition, for the recuperation of arsenic from contaminated media, new methods on identification and speciation of different form of arsenic have been developed with the aim to improve the levels of sensibility, speed and efficiency on measurements (Thotiyl et al., 2012). doi: 10.1016/j.jiec.2014.05.029, Mahmoud, M. E., Ali, S. A. Bidentate complexation modeling of heavy metal adsorption and competition on goethite. Secondly, and from a commercial perspective, research on composite adsorbents should be addressed toward their production on a larger scale, competitive in sorption capacity and operating costs. Res. 47, 65366544. Polym. JS thanks to DICYT from USACH (Grant No 021741SP). doi: 10.1016/j.impact.2016.09.004, Zhao, X., Lv, L., Pan, B., Zhang, W., Zhang, S., and Zhang, Q. Polymers such as poly[2-(acryloyloxy)ethyl]trimethylammonium chloride [P(ClAETA)] and poly(ar-vinylbenzyl)trimethylammonium chloride[P(ClVBTA)] were prepared and used in LPR technique to remove arsenic. It is remarkable that the high efficiency of the polycation is kept constant in the recuperation of As(V) species, even at strong higher arsenic concentrations. At pH 8, As(III) is found anion-dissociated salt in equilibrium with monovalent anions (H2AsO3-). Sorption enhancement of lead ions from water by surface charged polystyrene-supported nano-zirconium oxide composites. The maximum retention capacity of PDDA was 33 mg Cr/g polymer at pH 9.
Another similar hybrid was prepared using aluminum oxyhydroxide as the inorganic moiety (Prez et al., 2016). Reactive Funct. J. London: CRC Press. The polymer amount is 0.2 mmol, and the absolute amount of As(V) ions is 0.01 mmol. The LPR technique easily allows the separation of several species (metal ions, metalloids and organic pollutants), which are bonded to water-soluble polymers. Data 58, 11411150. Stuetz, R. M., and Stephenson, T. (2009). NanoImpact 3, 2239. Compendium of Chemical Terminology. 166, 923931. Macromol. 4, 21642167. Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles. Hazard. Water Treat. Removal of heavy metal ions by dithiocarbamate-anchored polymer/organosmectite composites. A review on polymerlayered silicate nanocomposites. Adsorption of Ni(II) from aqueous solution using oxidized multiwall carbon nanotubes. Cancer Ther. Eng. Sci. Novel amidoamine functionalized multi-walled carbon nanotubes for removal of mercury(II) ions from wastewater: combined experimental and density functional theoretical approach. Arsenate adsorption by hydrous ferric oxide nanoparticles embedded in cross-linked anion exchanger: effect of the host pore structure. 39, 14981525. Appl. doi: 10.1016/j.seppur.2017.02.008, Ca, F., Strauss, M., Clemente, Z., Rodrigues Neto, L. L., Lopes, J. R., Alencar, R. S., et al. Polym. Sep. Purif. Ion Exchange Materials Properties and Applications. 51, 353361. J. Appl. Future trends concerning to LPR technique involve the developments of hybrid methods. BU update the literature and wrote about nanocomposites. Tech.
102, 26772684. Mater. Polym. doi: 10.1021/acsami.5b09832, Li, J., Xiao, H., Kim, Y. S., and Lowe, T. L. (2005). Water Res. 53, 48384849. 168, 14301436. (2000). Technol. Enhanced swelling and adsorption properties of AAm-AMPSNa/clay hydrogel nanocomposites for heavy metal ion removal. Chem. doi: 10.1016/j.progpolymsci.2009.09.003, Stafiej, A., and Pyrzynska, K. (2007). (2006). Res. Sci. doi: 10.1021/ie401997g, Thotiyl, M. M. O., Basit, H., Snchez, J. 51, 127187. Hazard. (2016). doi: 10.1016/j.mseb.2013.03.011, Alexandratos, S. D. (2009). J.
The preparation of copolymers can be an effective option to modulate the selectivity and maximum retention capacity. (2003). Toxicol. J. Chem. Ind. Total Environ. Chem. Eur.
Prog. doi: 10.1089/ees.2013.0412, Pan, B., Li, Z., Zhang, Y., Xu, J., Chen, L., Dong, H., et al. Preclinical Clin. Organic/Inorganic hybrid network materials by the SolGel approach. Hybrid anion exchanger with dispersed zirconium oxide nanoparticles: a durable and reusable fluoride-selective sorbent. J. 28, 173208. doi: 10.1016/j.cej.2011.08.036, Wang, X., Fan, Q., Yu, S., Chen, Z., Ai, Y., Sun, Y., et al. 383, 130139. Clay Sci. 69, 881898. Polym. separating sieving sand gravel insoluble mixtures mixture materials soluble science examples filtering evaporating k8schoollessons (2003). doi: 10.1016/j.cej.2016.12.122, Rajput, S., Singh, L. P., Pittman, C. U. Jr., and Mohan, D. (2017). Synthesis, characterization and application of ethylenediamine-modified multiwalled carbon nanotubes for selective solid-phase extraction and preconcentration of metal ions. doi: 10.1002/app.26737, Rivas, B. L., Aguirre, M. D. C., and Pereira, E. (2006). The results revealed that is possible to remove and concentrate copper from aqueous solution by LPR with different water-soluble polymers and then reduce chemically copper to obtain cuprous oxide in all of the samples (Chou et al., 2018). Ahmadi, A., Heidarzadeh, S., Mokhtari, A. R., Darezereshki, E., and Harouni, H. A. doi: 10.1021/je301168m, Zhang, Y., Wu, B., Xu, H., Liu, H., Wang, M., He, Y., et al. Colloid Interface Sci. High sorption of U(VI) on graphene oxides studied by batch experimental and theoretical calculations. Simultaneous removal of Cu, Mn and Zn from drinking water with the use of clinoptilolite and its Fe-modified form. Infrared spectroscopy showed symmetric stretching vibrations sym(COO) at 1,405 cm1 and stretching asymmetric asym (COO) at 1,600 cm1 holding some free carboxylate COO.
Prog.
doi: 10.1016/j.progpolymsci.2014.03.001, Hua, M., Yang, B., Shan, C., Zhang, W., He, S., Lv, L., et al. Using the sorptiondesorption process, the results indicated that this PDDA can release Cr(VI) and be regenerated. At pH 7, the retention capacities for all of the metal ions were maximized (Cd(II) 99%, Zn2+ 98%, Cu(II) 100%, Co(II) 98%, and Ni(II) 100%), with the exception of Pb(II) and Cr(III), which showed no retention. Eng. The tin contents added were 3, 5, 10, and 20 wt %.
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