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Research Article pubs.acs.

org/journal/ascecg

Magnetic Nanoparticle Adsorbents for Emerging Organic Contaminants
Yuxiong Huang and Arturo A. Keller*
Bren School of Environmental Science and Management, University of California, Santa Barbara, California 93106, United States ABSTRACT: The recognition that pharmaceuticals, personal care product chemicals, and endocrine disruptors can cause deleterious effects has led to search new approaches for removing them from contaminated waters. The emergence of tailored nanomaterials, with magnetic properties and high adsorption capacity for a wide range of compounds, provides a new tool to deal with these complex emerging organic contaminants (EOCs). Magnetic permanently confined micelle arrays (Mag-PCMAs) synthesized with cationic surfactants can provide several sorption mechanisms for the multifunctional EOCs. The sorption onto Mag-PCMAs of seven EOCs and two more conventional contaminants was studied. The results indicate high sorption capacity for many of the EOCs. However, because of the complex nature of these EOCs, it is not possible to predict their adsorption based on a single physicochemical characteristic such as Kow or pKa. Sorption kinetics are relatively fast, within the typical range for water treatment processes. The low energy required for the synthesis of MagPCMAs, relatively low cost (∼$4/kg), ease of recovery with a magnetic field, and regenerability make them a much more sustainable option than more traditional approaches for removing EOCs, such as high energy granular activated carbon adsorption or advanced oxidation processes. KEYWORDS: Mag-PCMAs, Regeneration, Pharmaceuticals, Octanol−water partitioning, pKa

INTRODUCTION Recent attention has been directed at chemicals that are historically unregulated or not commonly regulated as contaminants but have the potential to enter the environment and cause known or suspected adverse ecological and human health effects, such as pharmaceuticals, personal care products, surfactants, various industrial additives, and endocrine disruptors, including hormones.1−3 These chemicals are collectively defined as emerging organic contaminants (EOCs) (http://toxics.usgs.gov/regional/ emc). The presence of these synthetic chemicals in the wastewater or surface water may contaminate ecosystems and surface and drinking water supplies. Recent studies have shown that EOCs may have biological effects and even potential ecotoxicological impacts on invertebrates (such as daphnids), fish, algae, mussels, and also human embryonic cells.4−10 To date, most of the studies have focused on the occurrence and/or fate of EOCs in surface waters11−15 and/or wastewater.1,16−19 However, there are few studies on approaches to remove EOCs from aqueous media. Therefore, the development of technologies to remove legacy and emerging organic contaminants from water is of great importance. In recent years, magnetic particles have received a lot of attention as powerful adsorbents because their inherent superparamagnetic properties make them desirable for magnetic field assisted separations.20−23 For instance, magnetic iron oxides (Fe2O3 and Fe3O4) have been reported as potential adsorbents for the removal of pollutants from aqueous media.24−27 The surface characteristics of the sorbents are very important to the effectiveness of the adsorption process. Because sorption
© 2013 American Chemical Society

of organic chemicals can be enhanced by coating of surfactants onto the sorbent, in a previous study we synthesized magnetic permanently confined micelle arrays (Mag-PCMAs) with a magnetite core and a silica porous layer that permanently confines surfactant micelles within the mesopores.28 The magnetic core allows for rapid separation of the Mag-PCMAs from solution by applying a magnetic field. Mag-PCMAs have been applied to the removal of very hydrophobic compounds,28 natural organic matter,29 and oxyanions.30 The objective of this study is to determine the effectiveness of Mag-PCMAs to remove EOCs from water. For comparison, two legacy contaminants (e.g., ethylbenzene, 2-chlorophenol) were also evaluated. The microenvironment of the interactions between the mesoporous layers of the Mag-PCMAs and the multiple binding sites on EOCs make it a significant study for sorbents in complex chemical environments, such as water treatment. Mag-PCMAs have low energy requirements in their synthesis, use, and regeneration, compared to other adsorbents such as granular activated carbon (GAC), resulting in a much more sustainable material.

Chemicals. Tetramethyl ammonium hydroxide (TMAOH) (25 wt % in water), 3-(trimethoxysily)propyl-octadecyldimethyl-ammonium Special Issue: Sustainable Nanotechnology Received: February 15, 2013 Revised: May 10, 2013 Published: May 14, 2013
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dx.doi.org/10.1021/sc400047q | ACS Sustainable Chem. Eng. 2013, 1, 731−736

MATERIALS AND METHODS

250 mm. and M is the mass of dry Mag-PCMAs (g). MD) or a UV−vis spectrometer (BIOSPEC-1601. methanol. The concentration of the sample was measured at the end of 5. Scanning Electronic Microscopy. D-gluconic acid sodium salt.11 4. pull force: 40. Batch Sorption of Emerging Organic Contaminants. 90. U. Ethylbenzene and 2-chlorophenol were purchased from Fisher Scientific (Pittsburgh. Preliminary experiments indicated that more than 99% of adsorption occurred within the first 120 min.29 9.170 250. sulfamethoxazole. Maghemite iron(III) oxide nanoparticles were dispersed in where C0 and Ce are the initial and equilibrium concentration of EOC in the liquid phase (mg/L).6 3.0 mg of Mag-PCMAs was mixed with 20 mL of a given organic contaminant in 20 mL vials. HPLC was used for the analysis of L-DOPA. a cationic surfactant. 2-chlorophenol at Figure 1. Maghemite iron(III) oxide nanoparticles (30 nm in diameter) were purchased from Alfa Aesar (Ward Hill. Each instrument was used to determine the final concentration of organic contaminants after adsorption occurred. Then the Mag-PCMAs particles with adsorbed contaminants were separated from the mixture with an Eclipse Magnetics N821permanent hand-held magnet (50 mm ×50 mm ×12. Shimadzu.0. Next.17 0. 1. 15. Properties of Compounds for Sorption Studies compound 2-chlorophenol atenolol D-gluconic ethylbenzene gemfibrozil L-DOPA methyl orange succinic acid sulfamethoxazole molecular mass (g/mol) 128. MO. The ultraviolet detector monitored the absorbance at 261 nm for L-DOPA. Shimadzu.2 5. which was determined to be sufficient to reach the adsorption equilibrium.560 266.336 218. DGU-14A degasser. Methyl orange and l-3-(3.8 g.S.0 mL/min. and 180 min. This three-step preparation of Mag-PCMAs is illustrated in Figure 1. (A) Mag-PCMA particles are introduced into a vial containing contaminated water. ammonia (28%).ACS Sustainable Chemistry & Engineering chloride (TPODAC) (72 wt % in methanol). 732 Figure 2.S. The solid-phase concentrations were determined by mass balance. was added to the maghemite suspension under constant stirring. U. The analyses were performed at a constant flow rate of 1. 5 mL of 28% ammonium hydroxide were added for base catalyzed sol−gel hydrolysis of TEOS (1.47 4. 40 mL of TMAOH solution (25% by weight) under constant mixing overnight to activate the surface. qe is the equilibrium concentration of contaminants adsorbed on the unit mass of MagPCMAs (mg/g).330 118. The three steps are done at room temperature (22 °C). The synthesis procedure for Mag-PCMAs was improved compared to the previous study to improve yield and reduce the use of ethanol. solutions with varying initial concentrations were treated with the same procedure as above at room temperature. MD). U.).59 0. All chemicals were used as received. Two instruments were used: a high performance liquid chromatography HPLC system (SPD-M10AVP.00 3. and succinic acid disodium salt were purchased from Sigma-Aldrich (St. inner diameter. 120.org/10. A total of 2. The contaminant concentrations ranged from 10 to 3000 mg/L.7 60. dx. gemfibrozil.A. Eng.00 kV. 243.).139 106.).7 − 4. PA. The HPLC analyses were carried out with a mobile phase comprised of 30% methanol/70% water. Beligum). 30.S.7 3.279 log10 octanol−water partition coefficient (log10 Kow) 2. Research Article Table 1. Then 0. All experiments were conducted at pH 7.A.190 327. Scanning electronic microscopy (SEM) imaging was performed under vacuum on an FEI XL40 FEG digital scanning microscope using an accelerating voltage of 5.1 mL) to cross-link the surfactant onto the magnetic iron core.333 197.68 −0. respectively.28 The core−shell structured Mag-PCMAs were synthesized through a solvothermal reaction.1021/sc400047q | ACS Sustainable Chem. 731−736 . Adsorption kinetics were determined by batch experiments. The equilibration time was 24 h uniformly. MA.1 N) To develop adsorption isotherms. Relevant physicochemical properties for the contaminants are presented in Table 1. Mag-PCMA synthesis is done with stepwise reagent addition. according to eq 1 qe = V × (C0 − Ce) M (1) Synthesis of Mag-PCMAs. and SPD-M10AVP diode-array detector.89 pKa 8. a Sil-10AF autosampler.090 253. V is the volume of solution.75 8. A TSKgel ODS-120A column (length.5 mm. tetraethyl orthosilicate (TEOS). The UV−vis spectrometer was used to monitor the concentration of organics in water at the absorption maximum for each compound: methyl orange at 400 nm.77 0. 2013.6 mm) was used. SEM of (A) Mag-PCMA at 71281X and (B) Mag-PCMA at 8910X.28 0. and the Mag-PCMAs concentration were 100 mg/L. atenolol. Figure 3.5 mL of TPODAC.doi.16 −6.A.4-dihydroxyphenyl)alanine (L-DOPA) were purchased from Acros Organics (Geel. The initial concentration of contaminant was 100 mg/L in all cases. without further purification. 4. These vials were shaken in an end-over-end shaker on Dayton-6Z412A Parallel Shaft roller mixer with a speed of 70 rpm at room temperature. demonstrating the rapid removal of Mag-PCMAs from the suspension within seconds of applying a magnetic field. which is cooperative assembly of silica oligomers and TPODAC on the Fe2O3 nanoparticles. Analysis by UV-Spectrophotometry and HPLC. (B) A permanent magnet is placed at the bottom of the vial to attract the magnetic particles. Louis. ethylbenzene at 261 nm. The HPLC system was equipped with two LC-10AT VP pumps. Silica is interspersed between the surfactant and magnetite covalently securing the micelles to the iron core and leaving void space for contaminant sorption.

731−736 . 1. (B) D-gluconic. The solid lines represent model fits based on the best model for each compound. (H) 2-chlorophenol.1021/sc400047q | ACS Sustainable Chem. (E) succinic acid.doi. Eng.org/10. Noncompetitive sorption onto Mag-PCMAs across a concentration range for (A) atenolol. (G) methyl orange. (C) gemfibrozil. and (I) ethylbenzene. (D) sulfamethoxazole. 2013.ACS Sustainable Chemistry & Engineering Research Article Figure 4. (F) L-DOPA. 733 dx.

988 1. ■ control their affinity for the cationic TPODAC surfactant.999 0. Sorption onto Mag-PCMAs for various compounds as a function of log Kow. RESULTS AND DISCUSSION Mag-PCMA Characterization. and L-DOPA were fitted using a nonlinear exponential model32 to provide a better fit log q = n log Ce + n2(log Ce)2 + log K f (3) On the basis of the equilibrium sorption concentrations.272 0.467 −0.99 or greater. D-gluconic acid is not included because it represents a major outlier with a log Kow of −6.55 × 10−4 3. except for ethylbenzene. 1. The energy requirements for the separation of the magnetic particles is minimal.467 0.219 n n2 n n2 n n2 n n2 n n2 4.596 0.945 8.doi.1021/sc400047q | ACS Sustainable Chem.257 0. Repeated adsorption experiments for ethylbenzene resulted in similar results.102 0.604 0.16 −0. succinic acid at 218 nm.72 −3.204 0.999 0.966 1. dx.999 0.917 0. Figure 4 presents the experimental results for the noncompetitive sorption for each compound for the range of concentration studies.0.226 11. While for more conventional non-ionic and contaminants such as petroleum hydrocarbons and chlorinated solvents.080 1. SEM images show the hydrated particles are 600 nm to 1 um in size (Figure 2). removal was strongly correlated with the Kow of the compounds. particularly if a permanent magnet is used. ethylbenzene.104 95% UCL for n 0.17 −0. with a very high recovery of the Mag-PCMAs.104 95% LCL for n 0.34 1. 731−736 .81 −9. Methyl orange was used to evaluate the adsorption kinetics onto Mag-PCMA.48 1. there is a strong correlation between removal efficiency and the octanol−water partitioning coefficient (Kow).0685 0. Fitted Parameter Values for Each Compound in Non-Competitive Sorption compounds D-gluconic Research Article n 0. q. succinic acid. 2-chlorophenol. Ce is the equilibrium concentration of contaminant in solution (mg/L). and n is a measure of adsorption intensity (dimensionless).ACS Sustainable Chemistry & Engineering Table 2.931 1.50 Kf 0. Calibration curves were performed daily with a regression (R2 value) of 0.20 21.277 0. removal rate was found to decrease with hydrophobicity. Noncompetitive Sorption Studies. their adsorption onto Mag-PCMAs generally increases with pKa (Figure 6).295 0.627 −0.30 The EOC present multiple characteristics that 734 major outliers.627 −0. a common indicator of hydrophobicity (Figure 6).967 0. Eng.256 31.28 and for anionic compounds removal efficiency can be predicted by their Gibbs free energy of adsorption.867 0.339 0. Table 2 summarizes the fitted values from all compounds. The Freundlich isotherm was used because it provided a better fit than linear or Langmuir models.93 nm.173 0.917 0. D-glueonic at 208 nm. The trend is much less conclusive than for a sequence of hydrophobic organic contaminants where in fact adsorption increases with hydrophobicity. Kf is the Freundlich adsorption constant (mg1−n g−1 Ln).967 0.622 −0. Additionally.628 0.34 1.50 succinic acid 2-chlorophenol ethylbenzene methyl orange 272. atenolol at 274 nm.104 log Kf 95% LCL for log Kf 95% UCL for log Kf −0.257 0.47 Exponential Model −3.9 1.467 0.589 0. In general. In general the amount sorbed decreases with increasing Kow (Figure 5). with L-DOPA and D-gluconic acid representing where q is the amount of contaminant adsorbed at equilibrium (mg/g).999 1 atenolol gemfibrozil sulfamethoxazole L-DOPA Freundlich Model −0. For ionizable compounds.3 1. indicating that some additional adsorption mechanism must be involved for this compound.102 0.997 1 1 0. sulfamethoxazole at 268 nm.917 0. Adsorption Kinetics for Methyl Orange.49 2.080 0.080 1. Figure 3 presents the separation of Mag-PCMAs from the suspension using a simple magnet.627 −0. The large number of −OH groups on both of these compounds results in very different behavior than the other compounds studied.50 0. at a given Ce Mag-PCMAs exhibited the highest sorption capacity for L-DOPA and the lowest for D-gluconic acid.257 0.867 0.8 30.945 1. 2013.628 0.34 1.21 1. Further work will be done with a broader range of compounds to elucidate more clearly the relationships.org/10. linearized by taking the logarithm of both sides of the equation31 log q = log K f + n log Ce (2) Figure 5.550 R2 0.628 0.211 −2.304 0. as well as the fit of a Freundlich isotherm.102 0.299 0.867 0. The Freundlich parameters Kf and n were determined from the intercept and slope of eq 2.260 9. and gemfibrozil at 275 nm. although the behavior is not easily predictable based on this physicochemical characteristic alone.08 1. The dispersed Mag-PCMAs can be separated within a few seconds from the suspension.967 0.24 0. For non-ionic compounds.15 −0.999 0.34 1.85 0.

239. Eng. T. The most likely mechanisms of adsorption of organic contaminants onto Mag-PCMAs are hydrophobic interactions. and electrostatic interactions. but synthesis of GAC requires heating the carbon source several hundreds of degrees to activate the carbonaceous surface. convenient. 358.e. Barcelo. Desalination 2009. hydrogen bonding. Spain). Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment. 158. M. Sorption onto Mag-PCMAs for various compounds as a function of pKa. almost all of the methyl orange was adsorbed. 2010. Salim. The regeneration of Mag-PCMAs. Notes ■ REFERENCES Figure 7. J. Figure 7B shows the evident color change in the mixture solution with the passage of time indicating the concentration of methyl orange decreased quickly. M. K. progestogens and polar pesticides in sewage treatment plant effluents. 1. S... considerable energy. The authors declare the following competing financial interest(s): The corresponding author has a minor interest (less than 1%) in a start-up company that has taken the synthesis process to a precommercial level and is building prototype treatment systems for the industry.. it is not easy to predict the adsorption capacity simply on the basis of one physicochemical property (e. Thomas. 2008. Environ. J. and the Mag-PCMAs with adsorbed organic contaminants can be easily removed from water via magnetic separation.. i. 2013.doi. Analysis and occurrence of pharmaceuticals. All ionizable compounds are considered.g... It is expected that the Mag-PCMAs will have potentially wide application in the removal of emerging organic contaminants from water.28.edu. The Mag-PCMAs perform well with a wide range of different organic contaminants with different solubility and pKa. J. CONCLUSIONS Mag-PCMAs with a core−shell structure are fast. This is in part because manufacturing CNTs requires high pressure and temperature.. Kollner. Granular activated carbon (GAC) is less than $1/kg. Because all of these mechanisms are at play for these mixed functionality compounds. The synthesis procedure for Mag-PCMAs is simple and requires low energy and relatively low cost (∼$4/kg).. E-mail: keller@ bren. (4) Hoeger. Bodour. Fax: +1 805 893 7612.1021/sc400047q | ACS Sustainable Chem. Martin-Alonso. Hitzfeld. D.ucsb. B. river water and drinking water in the Llobregat river basin (Barcelona. (A) Methyl orange equilibration kinetics. A. R. and oxyanions to consider emerging organic compounds. R. Hernando.. with a cost of $500−1000/kg. natural organic matter. D. M. de Alda. (3) Murray. Increasing the input energy can shorten the time needed for equilibrium. Further work will be done with a broader range of compounds to elucidate more clearly the relationships.ACS Sustainable Chemistry & Engineering Research Article Figure 6. ■ AUTHOR INFORMATION Corresponding Author *Tel: +1 805 893 7548. A. M. M. A review of the effects of emerging contaminants in wastewater and options for their removal. A. presented in previous studies. Water-borne diclofenac affects kidney and gill integrity and selected immune dx... Dietrich. This study has extended the application of Mag-PCMAs from removing very hydrophobic compounds. B. F. N. 112− 123.30 can be done at room temperature using ethanol or methanol to desorb the low Kow compounds or by changing pH for the ionic compounds. Within the first 60 min. given the high sorption capacity for this compound. 229−246. estrogens. with minimal additional sorption after 2 h (Figure 7A). (2) Bolong.org/10. 731−736 . Kow or pKa). and efficient sorbents for removing rather soluble organic contaminants from water. 3462−3471. Note that the image was made after 735 (1) Kuster. D. Petrovic. This can be compared to carbon nanotubes (CNTs) that have been considered as adsorbents. (B) Sorption time sequence.. even for an initial concentration of 100 mg/L. E. Sorption occurred rapidly. ■ concentrating the Mag-PCMAs at the bottom of the vial using a permanent magnet. M. including pharmaceuticals and personal care compounds. Matsuura... B. Pollut. Hydrol.. Ismail.

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