Removal of estrone from water by adsorption on zeolites with regeneration by direct uv photolysis

Worcester Polytechnic Institute

Removal of Estrone From Water by Adsorption on Zeolites with Regeneration by Direct UV PhotolysisHuajing Wen John A. Bergendahl Robert W. ThompsonWorcester Polytechnic Institute, [email protected] Follow this and additional works at: Suggested CitationWen, Huajing , Bergendahl, John A. , Thompson, Robert W. (2009). Removal of Estrone From Water by Adsorption on Zeolites withRegeneration by Direct UV Photolysis. Environmental Engineering Science, 26(2), 319-326.
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ENVIRONMENTAL ENGINEERING SCIENCEVolume 26, Number 2, 2009 Mary Ann Liebert, Inc.
DOI: 10.1089/ees.2007.0319 Removal of Estrone from Water by Adsorption on Zeolites with Regeneration by Direct UV Photolysis Huajing Wen,1 John A. Bergendahl,1,* and Robert W. Thompson2 1Department of Civil and Environmental Engineering, Worcester Polytechnic Institute, Worcester, Massachusetts. 2Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester, Massachusetts. Received: November 20, 2007 Accepted in revised form: March 27, 2008 Estrone is an endocrine-disrupting compound (EDC) that is suspected to have adverse effects on aquatic or-ganisms. This work investigated the removal of estrone from water by adsorption onto hydrophobic molecu-lar sieve zeolites followed by ultraviolet light (UV) photolysis to destroy the adsorbed estrone. A solvent-freeanalytical method employing solid phase micro-extraction (SPME) and gas chromatography (GC-FID) was uti-lized to analyze low estrone concentrations in water. Two types of zeolites, dealuminated Y (DAY) and sili-calite-1, were evaluated for adsorption capacity and compared with Centaur® activated carbon (CAC). DAYshowed the highest adsorption capacity, while silicalite-1 was the least effective in removing estrone. More-over, DAY required four hours to reach adsorption equilibrium; much less than the eight days needed for CACto reach equilibration. The Freundlich adsorption isotherm was found to best represent the data for adsorptionof estrone on DAY. UV at   254 nm degraded estrone in water much more effectively than long-wave UV(  365 nm). Regeneration of the contaminant-saturated DAY was accomplished with   254 nm UV light.
Key words: adsorption; estrone; endocrine disrupting compound; isotherm; UV; zeolites
nol ring of these molecules that possibly interacts with es-trogen receptors. Due to their extremely high biological po- ENDOCRINE-DISRUPTINGCOMPOUNDS(EDCS)are suspected of tency, a number of experiments have shown that trace
causing adverse health effects in organisms by interfer- amounts of estrogens, as low as ng/l, are capable of exert- ing with the normal function of hormones and the way hor- ing biological effects on aquatic organisms (Purdon et al., mones control growth. EDCs include natural and synthetic 1994; Arcand-Hoy et al., 1998; Kramer et al., 1998; Panter et hormones, some industrial chemicals, and some pesticides.
al., 1998; Routledge et al., 1998; Thorpe et al., 2003). Through More than 160 compounds have shown some evidence of en- excretion, female and male mammals are the primary source docrine disruption (Commission of the European Commu- for the natural estrogens (Adlercreutz et al., 1986; Johnson et nities, 1999). The early discoveries that certain compounds al., 2000). Synthetic estrogens are present in contraceptives can mimic the endogenous hormones of animals can be and other drugs used for treatment of cancers or hormonal traced back to the 1930s (Walker and Janney, 1930; Cook et disorders. They enter natural waters through discharges of al., 1934). In 1946, Schueler explained that molecular config- wastewater, primarily from wastewater treatment facilities.
urations of natural and synthetic compounds influenced the Reports from the United Kingdom and the United States in degree of estrogenic and androgenic bioactivity in rodents the 1990s indicated that fish living below wastewater treat- (Schueler, 1946).
ment plants had reproductive abnormalities (Purdon et al., Three natural estrogens, estrone, 17-estradiol, and estriol, 1994; Bevans et al., 1996; Folmar et al., 1996; Harries et al., and one synthetic estrogen, 17-ethynylestradiol, display the 1996; Jobling et al., 1998). Conventional wastewater treatment strongest estrogenic effects according to many reports (Des- plants can remove about 85% of 17-estradiol and 17- brow et al., 1998; Snyder et al., 1999; Snyder et al., 2001; ethynylestradiol and 70% of estrone on average (Johnson and Tanaka et al., 2001). This could be due to the common phe- Williams, 2004). However, the fraction that is not removedduring treatment is still able to pose adverse biological ef-fects in aquatic systems. In addition, part of the removed es- *Corresponding author: Department of Civil and Environmental En- trogens can accumulate in sludge from wastewater treatment gineering, Worcester Polytechnic Institute, 100 Institute Road, plants, and may potentially cause contamination of soil and Worcester, MA 01609, USA. Phone: 508-831-5772; Fax: 508-831-5808;E-mail: [email protected] ground water if that sludge is used as soil amendments or

TABLE 1. PHYSICAL AND CHEMICAL PROPERTIES OF ESTRONE (Wilcox and (Lai et al., al., 2000) al., 2006) landfilled (Auriol et al., 2006). Consequently, a variety of granular activated carbon has pore diameters between 5–40 treatment technologies have been looked at for destroying Å, with most pores in the 5–20 Å range (Merenov et al., 2000).
or removing estrogens from water such as: ozonation (Nak- All three of these samples were used in our prior studies agawa et al., 2002; Ternes et al., 2003), TiO2/UV oxidation with other organic compounds (Giaya et al., 2000; Erdem- (Ohko et al., 2002), UV/H2O2 oxidation (Rosenfeldt and Lin- Senatalar et al., 2004; Koryabkina et al., 2007), thus providing den, 2004), UV/H2O2/Fe oxidation (Feng et al., 2005), degra- a basis for comparison. The adsorbents were first dried in an dation with MnO2 (Rudder et al., 2004), adsorption on acti- oven at 120°C for 12–14 hr, and then stored in a dessicator vated carbon (Fukuhara et al., 2006), UV (Liu and Liu, 2004) containing a supersaturated solution of CaCl2 in water. This and chlorination (Hu et al., 2003). Effective treatment tech- approach was expected to produce moisture equilibrium in nologies are needed for removing EDCs from water.
a saturated humidity atmosphere (Giaya et al., 2000; Giaya In this research, estrone was removed from water by ad- and Thompson, 2002; Erdem-Senatalar et al., 2004; Ko- sorption onto hydrophobic molecular sieves. Regeneration ryabkina et al., 2007).
of the saturated adsorbent by UV photolysis was also in-vestigated. Estrone was selected as the target compound for Adsorption tests this research due to its presence in wastewater effluents, and The adsorption data were obtained by using various ad- because of the relatively low removal effectiveness of estrone sorbent/aqueous solution ratios (10–315 mg adsorbent/L in current treatment plants (Johnson et al., 2000). The main water). Subsequent to 5 hr mixing on an orbital shaker (Lab- physical and chemical properties of estrone are presented in line Instruments, Inc.), 40 mL solutions were transferred to Table 1 and the chemical structure is shown in Figure 1. A 45 mL vials, and liquid-solid separation performed by cen- fast and solvent-free analytical method was utilized for trifugation for 10 min at 2000 RPM (Eppendorf 5804 cen- quantifying estrone in water. It consisted of solid-phase mi- trifuge, Eppendorf, Germany).
croextraction (SPME) followed by on-fiber silylation forpreparing the sample for gas chromatography (GC) analysis Solid phase microextraction/gas (Carpinteiro et al., 2004).
A solid phase microextraction (SPME) fiber with an 85 m Materials and Methods
film thickness polyacrylate coating (Supelco) was used for Water samples extracting and concentrating estrone from the aqueous sam-ples. The fiber was initially conditioned by baking in the in- Estrone-spiked water samples were prepared from pow- jection port of the gas chromatograph (Agilent Technologies, dered estrone (99%, Sigma-Aldrich), stirred for 4–8 hr, and Series 6890) at 300°C for at least 2 hr as recommended by the filtered through glass fiber filters (47 mm, 0.7 m pore size, manufacturer (Supelco). Extraction was performed in 45 mL Pall Gelman Laboratory). The aqueous samples were stored vials by immersing the SPME fiber in 40 mL aqueous sam- protected from light at 4°C until use. Stock estrone solutions ples containing the internal standard. The extractions were for GC standard curves were prepared by dissolving estrone conducted at room temperature (20°C  2°C) for 1 hr with in methanol (HPLC grade, Fisher Scientific). The estronestock solution was stored at 4°C until use and diluted withpurified water (Barnstead RO-Pure ST/E-pure system) tomake standard solutions for SPME-GC-FID calibration. Aninternal standard solution, deuterated 17-estradiol (d4)(2,4,16,16 –D4, Cambridge Isotope Laboratories), preparedby dissolving 5 mg in 50 mL methanol, was added to all sam-ples before GC quantification.
Dealuminated Y (DAY) (Zeolyst), silicalite-1 (Union Car- bide), and a granular activated carbon made from bitumi-nous coal (Centaur®, Calgon Corporation) were used as ad-sorbents. The pores of the zeolites are uniform in shape andsize as a result of the regular crystalline framework struc- Molecular structure of estrone (Wilcox and Val- ture. The pore sizes of the zeolites are listed in Table 2. The lieres, 2006).
TABLE 2. REMOVAL OF ESTRONE FROM WATER WITH 24 H ADSORPTION ONTO CAC, DAY, AND SILICALITE-1. INITIAL ESTRONE CONCENTRATION  1130 g/L Total specific Ave. largest pore pore volume dimensions, dL (Å) surface area et al., 2004) et al., 2004) (Merenov et al., 2000) (Zhao et al., (Zhao et al., stirring at 400 rpm. pH adjustment was not performed for these analyses as the samples were ca. neutral, and others Three samples, pure dry estrone, wet DAY, and DAY sat- had found that sample pH did not affect SPME extraction of urated with estrone, were each subjected to thermogravi- estrogens (Carpinteiro et al., 2004). After the microextraction metric analysis (TGA). All samples were heated in the TGA step, the fiber was exposed to the headspace of a 1.5 mL vial (TA Instruments TGA 2950 Thermogravimetric Analyzer) containing 50 L of N-methyl-N-(trimethylsilyl) trifluoroac- from 30 to 500°C at a heating rate of 10°C/min under a purge etamide (MSTFA) (derivatization grade, Sigma-Aldrich) that of nitrogen gas. Weight losses as a function of sample tem- converts estrone to its silyl derivative (Carpinteiro et al., perature were recorded.
2004). Derivatization was carried out at 60°C for 15 min inan oven before each GC injection.
Results and Discussion
The GC was equipped with a flame ionization detector (FID), and an Equity™—5 capillary column 12 m in length, Screening experiments using zeolites 200 m in nominal diameter with 0.33 m film thickness.
and activated carbon The inlet and detector temperatures were 280°C. Nitrogen Initial screening experiments were conducted to compare was used as the carrier gas at a constant flow of 0.8 mL/min.
the ability of the three sorbents to remove estrone from wa- Hydrogen gas and air at flow rates of 40 mL/min and 180 ter. The results are listed in Table 2, and show that DAY had mL/min, respectively, were used for the FID flame. The flow the greatest equilibrium removal of estrone (99%), while sil- rate of make up nitrogen gas was 19.2 mL/min. The GC oven icalite-1 was least effective (39%). The Centaur® activated was programmed as follows: 1 min at 80°C, ramped at carbon (CAC) removed 69%. Given that an estrone molecule 15°C/min to 260°C and held for 20 min. The SPME fiber was has a width of about 3.8 Å and length of about 10.8 Å (Wilcox allowed to desorbed in the GC inlet for 5 min at 280°C and and Vallieres, 2006), it might be expected that estrone would was heated for an additional 5 min at the same temperatureto avoid carry-over. The concentration of estrone in the sam-ple was determined from a linear standard curve after ad-justing for method sensitivity using the internal standard.
Blanks were included in each run, as well as spikes of knownconcentrations within the standard curve concentrationrange. The method detection limit was 1 g/L.
Degradation of estrone by ultraviolet light Irradiation by UV light using a short wavelength UV lamp (Model 11SC-1 Mercury Pen-Ray lamp, 254 nm, 6650 W/cm2) and a long wavelength UV lamp (36-380 Spec-tronics Corp., 365 nm peak, 1000 W/cm2) was performedin an annular volume between a quartz tube (ACE-7506-10,ACE Glass Inc., approximately 13 cm long and 1.2 cm di-ameter with 5 mm wall thickness), and a glass outer tube(ACE Glass Inc., approximately 11 cm long and 2.5 cm di-ameter with 2 mm wall thickness). Due to the limited vol-ume in this apparatus, 40 ml water samples were dividedinto 8 runs for irradiation. The contact times were 10 s, 20 s, Kinetics of adsorption of estrone on DAY (20°C); 30 s, 1 min, 3 min, 6 min, and 30 min.
two symbols represent duplicate runs.
not be prevented from the pores in all three samples. How-ever, DAY has a 3-D cage-like structure while silicalite-1 hasa 3-D channel structure. It is uncertain if their structural dif-ferences contributed to their quite different adsorbability.
BET surface areas also provide an indication of a sorbent'sability to remove contaminants. Higher BET surface areasusually provide for greater adsorbability, yet for estrone ad-sorption, CAC with a much greater surface area (Table 2) un-derperformed DAY. Silicalite-1 was eliminated from furtherstudy after the screening experiments due to its low equi-librium adsorption performance.
Kinetics of adsorption Kinetics experiments were carried out with DAY and CAC by placing the adsorbents and estrone in 45 ml vials and sac-rificing vials at predetermined times. The results of the ki-netic studies for DAY and CAC are shown in Figures 2 and Adsorption isotherm of estrone on DAY at 20°C.
3, respectively. The time for reaching adsorption equilibriumfor DAY was approximately 4 hr, while it took more thanone week for CAC to reach adsorption equilibrium. Due to the extremely long contact time for estrone to adsorb to CAC max is the saturation capacity in mg/g, and b is a only DAY was studied in more detail in subsequent experi- The fit of the data to the linearized Freundlich isotherm is shown in Figure 5. The high R2 value establishes that thereis a very good fit to the data. The R2 value for the fit of the DAY Adsorption Isotherm data to the linearized Langmuir model was 0.892, and is not The adsorption isotherm for estrone on DAY is presented shown here. However, it is worth noting that the saturation in Figure 4. The data were fitted to the linearized Freundlich capacity parameter, qmax, computed from the Langmuir and Langmuir adsorption models.
isotherm analysis was 74 mg/g, quite close to the limiting The linearized Freundlich model is: value observed experimentally.
The values found for the Freundlich constants were 1/n  1.10, and K  0.163 (mg/g)(L/g)1.10. The Freundlich con- stant K is thought to represent the adsorption capacity, and where qe is the mass in g of adsorbate (estrone) per mass 1/n the adsorptive energy between the adsorbent and the in g of adsorbent (DAY), Ce is the equilibrium concentration adsorbate. The higher the value for K, the stronger the ad- of estrone in water in g/L, and K and 1/n are Freundlich sorption capacity; while the smaller the value for 1/n, the stronger the adsorptive energy. Fukuhara et al. evaluated dif- The linearized Langmuir model is: ferent types of activated carbons for estrone removal fromwater (Fukuhara et al., 2006) (Table 3). They concluded that adsorption capacity increases with increases in specific sur- face area. This work is consistent with that observation asDAY has a smaller specific surface area than the activatedcarbons in Table 3, and performs less effectively from anequilibrium standpoint, yet has kinetics benefits over CAC(Figs. 2 and 3).
It was estimated that approximately 16% of the DAY pore volume was filled at saturation. This seemingly low level ofpore filling, noted by the plateau in the isotherm, might be hy-pothesized to be due to estrone existing as pure, crystal or pre-cipitated solid or quasi-solid estrone in the pore throats, block-ing the potential for higher loadings. Note the rather highmelting point for estrone (255°C), which is listed in Table 1.
Thus, at room temperature, estrone can be expected to be asolid. Since prior evidence has suggested that these hy-drophobic zeolites adsorb very little water (Giaya et al., 2000;Giaya and Thompson, 2002), estrone might be assumed to ad-sorb with very little water, and thus be essentially pure in theadsorbed state. That being the case, one might expect it to be-have as a solid or quasi-solid phase, making diffusion into thepores rather difficult. Secondly, Molecular Dynamics simula- Kinetics of adsorption of estrone on CAC (20°C); tions of a single estrone molecule in a DAY cavity revealed two symbols represent duplicate runs.
that the hydrogen atom in the –OH group (Fig. 1) hydrogen REMOVAL OF ESTRONE BY ADSORPTION ON ZEOLITES
Thermogravimetric analysis (TGA) Thermogravimetric analysis was conducted to help un- derstand the requirements for thermal regeneration of thesaturated DAY, and to elucidate the behavior of estrone inthe pores of the DAY with temperature increases. The resultsin Figure 7 show that the weight loss of pure estrone accel-erated at about 300°C, i.e., slightly above its melting point of255°C. A much slower weight loss continued to occur up to600°C. A boiling point for estrone does not appear to havebeen reported, so this slower weight loss may have resultedfrom thermal decomposition in the nitrogen environment.
Water in DAY started evaporating well below 100°C, andwas essentially completely vaporized once the samplereached about 110°C. The carrier gas undoubtedly enhancedwater vaporization at temperatures below its normal boilingpoint. The sample containing adsorbed estrone removedfrom water started losing weight as soon as heating began.
Plot of estrone on DAY adsorption data to lin- Weight loss up to 75°C was most likely water adsorbed earized Freundlich isotherm at 20°C.
loosely on the external surface of the DAY, facilitated, as be-fore, by the carrier gas. Subsequent weight loss due to es-trone was revealed by a slow weight loss up to 600°C, as be-fore.
bonded with oxygen atoms in the DAY structure, more or less Temperatures in the range of 250–400°C are typical for ze- anchoring it to the cavity (Yazaydin, 2007). The snapshot in olite-catalyzed organic reactions, and the DAY sample is Figure 6 shows very temporary and transient hydrogen bonds known to have small amounts of AlO T-sites, known to with three DAY oxygen atoms, which formed and broke very possess catalytic acidity that catalyzes some organic conver- quickly. However, the estrone molecule was never observed sions. Thus, it is likely that the gradual weight loss noted to hop to an adjoining cavity in these simulations. Therefore, here indicates that estrone experienced chemical degrada- it is suspected that the relatively low loading was due to the tion reactions in the DAY. This also would explain why isolation of estrone molecules to cavities near the external sur- weight loss of estrone in DAY began at lower temperatures faces of the DAY crystals.
than for the pure estrone.
Molecular Dynamics simulations of estrone in silicalite- Thus, using thermal regeneration to remove estrone from 1 were also carried out (Yazaydin, 2007), but are not shown the DAY pores one would expect to have to raise the tem- here. The observations in the silicalite structure were that perature to about 600°C for some period of time, an energy- estrone fit rather tightly in that pore system with little room intensive process. Incomplete removal of estrone from the for other estrone molecules, hydrogen bonding occurred DAY pores would be expected at lower temperatures.
frequently, and the estrone molecule seemed somewhattrapped in the pores. The estrone molecules did not move Direct UV irradiation to destroy estrone in water along the straight or zig-zag pores. The lower adsorptioncapacity of silicalite-1 observed in the experiments could be A 254 nm wavelength UV light (200 mJ/cm2) rapidly de- understood from these simulations to stem from the smaller stroyed estrone in water as shown in Figure 8. A reduction pore volume in comparison to the larger DAY pore vol- of 89.5% was reached in 30 seconds. Further UV fluence did not degrade estrone to lower than 75 g/L.
TABLE 3. COMPARISON OF FREUNDLICH CONSTANTS (C IN g/L AND q IN mg/g) FOR ESTRONE ADSORPTION ONTO VARIOUS ACTIVATED CARBONS AND DAY Total specific pore volume surface area [(mg/g)  (L/g)1/n] (Fukuhara et al., 2006) (Fukuhara et al., 2006) (Fukuhara et al., 2006) (Fukuhara et al., 2006) (Fukuhara et al., 2006)

Snapshot of estrone in a DAY cavity, based on Molecular Dynamics simulations (Yazaydin, 2007). The white atoms in the center cavity are the main hydrogen atoms of the estrone molecule. (Color image is available online at UV irradiation may mitigate the estrogenic impact of es- For comparison purposes, destruction of estrone was at- trogens (Ohko et al., 2002; Liu and Liu, 2004). Ohko et al. tempted with longer wavelength UV light. It was found that (2002) concluded that the phenol moiety may be the origin 365 nm UV light was not as effective at destroying estrone of photocatalytic oxidation and they presumed that the es- with only 10% destroyed in 6 min (360 mJ/cm2). This ob- trogenic activities of the intermediate products lacking a phe- servation is consistent with data presented by others. Liu and nol ring were negligible. Liu and Liu (2004) showed that pho- Liu found that long-wave light ( 365 nm) was less effec- tolysis of estrogens caused the breakage and oxidation of tive than short-wave UV light (  254 nm) for photolysis of benzene rings to produce products containing carbonyl estrone in aqueous solutions (Liu and Liu, 2004). Rosenfeldt and Linden reported that bisphenol A, ethinyl estradiol, and Thermogravimetric analysis (TGA) results for pure Estrone degradation in aqueous solution with UV estrone, DAY & water, and DAY & estrone.
light irradiation (  254 nm).
is used to treat wastewater, it generally requires a high con-sumption of UV energy due to continuous contact with alarge volume of water with low concentrations of contami-nation. The combined adsorption/UV process may have ad-vantages in treatment as the regeneration step can be per-formed with higher (adsorbed) contaminant concentrations.
We acknowledge WPI's Research Development Council for funding this research. We are grateful for assistance withthe TGA analyses from Ms. Marta Dabros, Prof. John Mac-Donald, and Prof. Venkat R. Thalladi in the Chemistry andBiochemistry Department at WPI. Prof. Jennifer L. Wilcoxand Mr. Peter Vallieres of the Chemical Engineering De-partment at WPI computed the molecular dimensions of es-trone. Dr. A. Ozgur Yazaydin completed the Molecular Dy- Equilibrium capacity after adsorption/UV (  254 namics simulations. Mr. Don Pellegrino in the Civil and nm) regeneration cycles.
Environmental Engineering Department at WPI assistedwith the experimental equipment used throughout thisstudy.
estradiol only adsorbed UV radiation in the range of 200-300 Author Disclosure Statement
nm (Rosenfeldt and Linden, 2004).
No competing interests exist.
UV regeneration of estrone-saturated DAY Irradiation with UV light at   254 nm was used to re- Adlercreutz, H., Fotsis, T., Bannwart, C., Hämäläinen, E., Bloigu, generate the estrone-saturated DAY by mineralizing the en- S. and Ollus, A. (1986). Urinary estrogen profile determina- trapped estrone. A similar strategy was used to regenerate tion in young Finnish vegetarian and omnivorous woman.
adsorbents containing chloroform and trichloroacetic acid in Journal Steroid Biochemistry 24, 289.
our previous work (Koryabkina et al., 2007). Figure 9 shows Arcand-Hoy, L. D., Nimrod, A. C. and Benson, W. H. (1998). En- adsorption equilibrium results for DAY regenerated using docrine-modulating substances in the environment: estro- UV irradiated for 6 and 30 min. These data are the accumu- genic effects of pharmaceutical products. International Journal lation of nine cycles of adsorption, followed by regeneration of Toxicology 17, 139.
with UV light. These results are compared to data from Fig- Auriol, M., Filali-Meknassi, Y., Tyagi, R. D., Adams, C. D. and ure 4, which represents DAY not previously exposed to es- Surampalli, R. Y. (2006). Endocrine disrupting compounds re- trone. While there is some scatter in the data for the regen- moval from wastewater, a new challenge. Process Biochemistry erated DAY, the data suggests that UV light was successful Bevans, H. E., Goodbred, S. L., Miesner, J. F., Watkins, S. A., in mineralizing estrone associated with the DAY pores. The Gross, T. S., Denslow, N. D. and Schoeb, T. (1996). Synthetic small variations in the data are most likely due to small loss organic compounds and carp endocrinology and histology in of the solid zeolite powder between cycles due to handling Las Vegas Wash and Las Vegas and Callville Bays of Lake Mead, Nevada, 1992 and 1995, US Geological Survey, WaterResource Investigations Report 96, 4266.
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