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Stability and removal of dexamethasone sodium phosphate from wastewater

using modified clays

Article  in  Environmental Technology · February 2014

DOI: 10.1080/09593330.2014.888097

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 PROOF COVER SHEET

Author(s): Rafik Karaman

Article title: Stability and removal of dexamethasone sodium phosphate from wastewater
using modified clays
Article no: TENT888097
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 Techset Composition India (P) Ltd., Bangalore and Chennai, India TENT888097 Page#: 11 Printed: 10/2/2014

Environmental Technology, 2014

http://dx.doi.org/10.1080/09593330.2014.888097
1 57
2 58
3 59
4 60
5 61
6 62
7 Stability and removal of dexamethasone sodium phosphate from wastewater 63
8 using modified clays 64
9 65
10 Saleh Sulaimana,b , Mustafa Khamisc,d , Shlomo Nire , Filomena Lelarioa , Laura Scranof , Sabino Aurelio Bufoa and 66
11 Rafik Karamana,b∗ 67
12 a Department of Science, University of Basilicata, Potenza 85100, Italy; b Department of Bioorganic Chemistry, Faculty of Pharmacy, 68
13 Al-Quds University, Jerusalem 20002, Palestine; c Department of Chemistry and Chemical Technology, Faculty of Science and 69
14 Technology, Al-Quds University, Jerusalem 20002, Palestine; d Department of Biology, Chemistry and Environmental Sciences, 70
15 American University of Sharjah, POB 26666, Sharjah, United Arab Emirates; e Department of Soil and Water Sciences, Faculty of 71
Agriculture, Food and Environment, Hebrew University of Jerusalem, Rehovot 76100, Israel; f Department of Mediterranean Culture,
16 72
University of Basilicata, Matera 75100, Italy
17 73
18 (Received 7 July 2013; accepted 20 January 2014 ) 74
19 75
Stability and removal of dexamethasone sodium phosphate (DSP) from wastewater produced at Al-Quds University Campus
20 were investigated. Kinetic studies in both pure water and wastewater coming from secondary treatment (activated sludge) 76
21 demonstrated that the anti-inflammatory DSP underwent degradation to its hydrolytic derivative, dexamethasone, in both 77
22 media. The first-order hydrolysis rate of DSP in activated sludge at 25◦ C (3.80 × 10−6 s−1 ) was about 12-fold larger than in 78
23 pure water (3.25 × 10−7 s−1 ). The overall performance of the wastewater treatment plant (WWTP) installed in the University 79
24 Campus was also assessed showing that 90% of spiked DSP was removed together with its newly identified metabolites by 80
the ultra-filtration (UF) system, which consists of a UF hollow fibre (HF) with a 100-kDa cutoff membrane as the pre-
Coll:

25 polishing stage for the UF spiral wound with a 20-kDa cutoff membrane. In testing other technologies, the effectiveness of 81
26 adsorption and filtration by micelle–clay (MC) preparation for removing DSP was ascertained in comparison with activated 82
27 charcoal. Batch adsorption in aqueous suspensions of the MC composite and activated carbon was well described by Langmuir 83
QA:

28 isotherms showing the best results for MC material. Filtration of DSP water solutions demonstrated a significant advantage 84
29 of columns filled in with a mixture of sand and MC complex in comparison with activated carbon/sand filters. 85
CE: FR

30 Keywords: dexamethasone sodium phosphate; wastewater treatment; activated sludge; activated charcoal; micelle–clay 86
31 complex; column filtration 87
32 88
33 89
34 Nomenclature chemical, physical and biological processes have been 90
35 DSP dexamethasone sodium phosphate developed, such as microbial degradation, filtration, adsorp- 91
36 FAC fine powder activated charcoal tion, coagulation and membrane separation. However, all 92
37 GAC granular activated charcoal these remediation methods have suffered from certain lim- 93
38 HF hollow fibre UF membrane itations and disadvantages such as high cost, poor removal 94
39 HP hydrolysis product efficiency and possibility of desorption.[1] This is an ever 95
40 MC micelle–clay complex growing problem including the so-called ‘emerging pollu- 96
41 ODTMA octadecyl trimethyl ammonium tants’, which comprise a large number of pharmaceuticals. 97
RO reverse osmosis For the past three decades, data have been accumulated on
42 98
SW spiral wound UF membrane the concentrations of pharmaceutical residues in drinking
43 99
UF ultra-filtration water.[2]
44 100
WWTP wastewater treatment plant The occurrence of pharmaceutically active substances
45 101
46 in the environment has become an important issue in the 102
47 last few years. These compounds along with their metabo- 103
1. Introduction lites, which can be even more harmful than the original
48 104
Despite the progress in water treatment methods, vary- compounds, are continuously released into the environ-
49 105
ing amounts of chemicals exist in what is referred to as ment, mainly through disposal of unused or expired drugs
50 106
‘clean’ water.[1] Organic contaminants in the environment, or directly from pharmaceutical discharges.[3]
51 107
especially in water, have become a major concern due to Pharmaceuticals are generally excreted after being par-
52 108
their toxicity. To remediate this pollution problem, various tially or completely converted to metabolites with enhanced
53 109
54 110
55 ∗ Corresponding 111
author. Email: dr_karaman@yahoo.com
56 112
© 2014 Taylor & Francis
 2 S. Sulaiman et al.

113 from the plant was investigated and the DSP degradation 169
114 products were identified. 170
115 Finally, to check for different tools to be used instead 171
116 of UF membranes, the effectiveness of micelle–clay (MC) 172
117 filter for removing DSP was ascertained and compared 173
118 with a filter filled with GAC. Besides, the DSP adsorption 174
119 equilibrium parameters and the adsorption Langmuir coef- 175
120 ficients were determined by using both MC and fine powder 176
121 activated charcoal (FAC) as the adsorbent materials. 177
122 DSP, 9-fluoro-11β,17-dihydroxy-16α-methyl-21-(pho- 178
123 sphonooxy) pregna-1,4-diene-3,20-dione disodium salt 179
124 (structure 1 in Scheme 1), a synthetic adrenocortical steroid, 180
Figure 1. Flow diagram schematizing the WWTP at Al-Quds
125 University. Sampling sites are indicated by numbers. UF/HF, is a white or slightly yellow, crystalline powder. It is highly 181
126 hollow fibre ultra-filtration membrane; UF/SW, spiral wound soluble in water and is exceedingly hygroscopic. It is widely 182
127 ultra-filtration membrane; RO, reverse osmosis; GAC, granular used to treat inflammation, allergy and diseases related to 183
128 activated charcoal filter. adrenal cortex insufficiency. DSP is also known to reduce 184
129 neointimal hyperplasia in arteries.[13,14] It is used for coat- 185
130 ing drug-eluting stents for local drug delivery to prevent 186
131 solubility in water, but a significant quantity of the par- restenosis [15–17] and is 5–14 times more potent than pred- 187
132 ent drug may also be excreted unchanged.[4] Most of nisolone and 25–75 times more potent than cortisone and 188
133 these compounds come either from domestic sewage or hydrocortisone.[18] The corticosteroids cause alterations in 189
134 from hospitals, or industrial discharges, and enter municipal metabolism of fats, proteins and carbohydrates, and affect 190
135 wastewater treatment plants (WWTPs). The removal effi- a range of organs in the body including the heart, mus- 191
136 ciency of WWTPs is influenced by the chemical properties cle and kidneys. Blood chemistry may change and there 192
137 of each specific compound to be removed, microbial activ- is decreased activity and shrinkage of the thymus gland, 193
138 ity in the activated sludge (AS) unit, use of membrane units adrenal glands, spleen and lymph nodes. The liver becomes 194
139 and environmental conditions realized in the plant.[5–7] enlarged, thyroid activity decreases and mineral is drawn 195
140 Recent studies have clearly shown that the elimina- away from bone. Muscle wasting occurs, and the immune 196
141 tion of pharmaceutically active compounds in munic- system is adversely affected causing the person to be more 197
142 ipal WWTPs is often incomplete,[8] with efficiencies susceptible to infections, especially of the eye.[13–17] DSP 198
143 ranging between 60% and 90% for a variety of polar is one of the most water-soluble adrenocorticosteroidal 199
144 compounds.[9–12] agents. It is, therefore, suitable for intravenous use and 200
145 To evaluate the efficiency of different traditional and particularly for ophthalamic formulations.[19] 201
146 innovative tools for the elimination of pharmaceutical The MC composite, which was used in this study, is pos- 202
147 residues, we are performing a series of water purifica- itively charged, has large surface area and includes large 203
148 tion experiments by using the WWTP installed at the hydrophobic domains.[20] Micelle–clay composites have 204
149 Al-Quds University in Palestine (Figure 1), which includes already been proven useful in the removal of about 20 205
150 sequential units, such as AS, ultra-filtration (UF), granular neutral and anionic pollutants.[20–25] 206
151 activated charcoal (GAC) and reverse osmosis (RO).[4] 207
152 Problems arising from the management of such a plant 208
153 can be referred to the capability of the AS unit to favour the 2. Experimental 209
154 bio-degradation of organic pollutants as well as the fouling 210
2.1. Materials and equipment
155 phenomenon affecting membrane units, which must be often 211
replaced with high costs. 2.1.1. Materials
156 212
157 In the present work, we are reporting about the efficiency All chemicals were of analytical grade. The clay used 213
158 of advanced wastewater treatment technologies adopted was Wyoming Na-montmorillonite SWY-2 clay; obtained 214
159 in the Al-Quds plant for the removal of ‘dexamethasone from the Source Clays Registry (Clay Mineral Society, 215
160 sodium phosphate’ (DSP), which was used as the model Colombia, MO, USA). Quartz sand (grain size 0.8–1.2 mm) 216
161 pharmaceutical compound due to its high solubility in water was obtained from Negev industrial minerals (Israel). 217
162 and large consumption in many Countries. Nevertheless, Octadecyl trimethyl ammonium (ODTMA) bromide was 218
163 because of the tendency of DSP to undergo hydrolysis in a obtained from Sigma–Aldrich. Pure DSP and its hydroly- 219
164 large range of pH, we were also concerned with the removal sis product dexamethasone (structure 2 in Scheme 1) were 220
165 of its hydrolysis product ‘dexamethasone’. obtained from Birzeit Pharmaceutical Company (Pales- 221
166 Aiming at the assessment of bacterial culture, which tine) with 99% purity, and both were used as received. 222
167 normally develops in the AS unit of Al-Quds WWTP, the FAC with particle size ≤ 60.0 μm, and GAC with parti- 223
168 stability of DSP in pure water as well as in the AS collected cle size ≤ 700.0 μm were obtained from Sigma (Sigma 224
 Environmental Technology 3

225 O 281
226 P O OH 282
227 O O Na 283
O HO Me OH
O
228 HO Me Na 284
229 OH Me Me 285
230 Me Me 286
231 287
F
232 F O 288
O
233 2 289
1
234 290
235 Scheme 1. Structures of DSP (1) and its hydrolysis product dexamethasone (2). 291
236 292
237 293
Chemical Company, USA). The powder was used for for both DSP and its hydrolysis product in pure water.
238 294
batch adsorption experiments while the granules were used The calibration curves were obtained with a determina-
239 295
in column experiments. Magnesium sulphate anhydrous, tion coefficient R2 of 0.9996 and 0.9998, respectively.
240 296
potassium dihydrogen phosphate as well as methanol and The repeatability of triplicate subsequent injections was
241 297
water for analysis (HPLC grade) were purchased from ranging from 98.8% to 99.5%, depending on the sam-
242 298
Sigma–Aldrich (Munich, Germany). High-purity diethyl ple concentration and type of analyte. The repeatability of
243 299
ether (>99%) was purchased from Biolab (Israel). morning/evening injections on the basis of 6-hours elapsed
244 300
For sample enrichment and purification, SPE 1 g C–18 time was ranging from 97.6% and 98.2%, and was also
245 301
6 mL disposable cartridges (Waters, Milford, MA, USA) affected by the concentration and type of analyte. Correction
246 302
were used. coefficients were used for experimental samples.
247 303
Calibration curves and repeatability trials were repeated
248 304
2.1.2. Equipment preparing new calibration solutions by using wastewater
249 305
Samples were shaken using Big Bill, (Banstaed/Themolyne, taken from the AS reservoir of Al-Quds WWTP. Results
250 306
USA). The disappearance of DSP and its hydrolysis product suffered from a major inaccuracy due to the variability
251 307
were determined by using a high-pressure liquid chromatog- of recovery percentages. The determination coefficients of
252 308
raphy system model 2695 HPLC from Waters (Israel), calibration curves were 0.9985 for DSP and 0.9989 for
253 309
equipped with a Waters 2996 Photodiode array. Data acqui- dexamethasone. Repeatability normally was not reduced.
254 310
sition and control were carried out using Empower™ The limit of detection, based on a signal/noise of 3, was
255 311
software (Waters, Israel). Analytes were separated on a 0.02 mg L−1 for DSP and 0.01 mg L−1 for dexamethasone.
256 312
4.6 mm × 150 mm C18 XBridge® column (5-μm particle The limit of quantification, based on a signal/noise of
257 313
size) used in conjunction with a 4.6 mm, 20 μm, XBridge® 10, was 0.06 and 0.03 mg L−1 for DSP and its hydrolysis
258 314
C18 guard column. product, respectively.
259 315
260 HPLC conditions: mixture of 0.01 M KH2 PO4 : 316
methanol (1:1; v/v) as mobile phase; flow rate of 2.2.1. Characterization of wastewater used
261 317
262 1.2 mL min−1 ; UV detection at a wavelength of 254 nm The wastewater was characterized before the experiments 318
263 Acrodisc® syringe filters with GHP membrane (hydrophilic according to American Public Health Association pro- 319
264 polypropylene 0.45-μm porosity) from Waters were always cedures [26,27] by performing measurements listed in 320
265 used for all analytical filtration requirements. The identifi- Table S1 (Supplementary material). 321
266 cation of DSP degradation products was performed using The initial relatively high values of COD and TSS may 322
267 a liquid chromatography system coupled to a hybrid lin- be attributed to residues of chemicals in the wastewater from 323
268 ear quadrupole ion trap–Fourier-transform ion cyclotron laboratories, which were not well removed by the secondary 324
269 resonance (FT-ICR) mass spectrometer (Thermo Fisher biological treatment. 325
270 Scientific, Bremen, Germany). Table S2 (Supplementary material) summarizes chem- 326
271 The advanced WWTP employed in this study is located ical, physical and biological characteristics of wastewater 327
272 at Al-Quds University-Palestine and was described in detail sampled from the AS reservoir of Al-Quds WWTP (sam- 328
273 elsewhere.[24] Normally, the effluent from this plant is pling site #2 in Figure 1). This table reveals that the 329
274 recycled for the irrigation of plants cropped in the field of wastewater contained high amounts of suspended solids 330
275 university campus. and large populations of bacteria, which are responsible for 331
276 the fouling phenomena affecting UF and RO membranes. 332
277 Moreover, high values of electrical conductivity and total 333
2.2. Methods dissolved solids are typical for municipal wastewaters and
278 334
279 Linearity of the proposed analytical method was verified by should be reduced if WWTP effluents are re-used for crop 335
280 analysing standard solutions in the range of 0.1–100 mg L−1 irrigation purposes. 336
 4 S. Sulaiman et al.

337 2.2.2. Efficiency of WWTP for DSP and dexamethasone 2.2.6. Column filtration experiments 393
338 removal Column filtering experiments were performed using 50:1 394
339 The efficiency of different treatment units was ascer- (w/w) mixtures of quartz sand and either ODTMA–clay 395
340 tained by spiking separately the secondary effluent with complex, or GAC, 20 cm layered in borosilicate columns 396
341 1.0 mg L−1 of either DSP or its hydrolysis product dex- of 25-cm length and 5-cm diameter. Each column con- 397
342 amethasone in the AS reservoir (1000 L). Samples were tained 13 g of complex, or GAC. The bottom of the column 398
343 collected from different locations of the WWTP as depicted was covered with 3-cm layer of quartz sand. Quartz sand 399
344 in Figure 1. Before analysis of DSP, 1 mg of KH2 PO4 was was thoroughly washed by distilled water and dried at 400
345 added to 100 mL of sample to stabilize pH, the acidic form 105◦ C for 24 h before its use. Solutions in pure water (1 L 401
346 of DSP and the ionic strength of the solution. SPE-C18 dis- each) containing different DSP concentrations (0.01, 1, 10 402
347 posable cartridges were used to pre-concentrate 10 mL of and 100 mg L−1 ) were passed through either MC or GAC 403
348 each sample by adsorption of analytes. A part (20 μL) of the columns (one column for each solution). In all cases, the 404
349 methanolic solution eluted from SPE cartridge was injected flow rate was 2.0 mL min−1 . Eluted fractions were collected 405
350 into the HPLC and analysed using the same conditions for in all column experiments and analysed. 406
351 the determination of both DSP and dexamethasone. Recov- All experiments reported in Sections 2.2.1–2.2.6 were 407
352 ery tests were performed using triplicate solutions of both performed in three replicates, and average values and 408
353 substances, and values ranging from 98% to 102% were standard deviations were calculated. 409
354 obtained. 410
355 411
356 3. Results and discussion 412
357 2.2.3. Stability of DSP 3.1. Efficiency of WWTP for DSP and dexamethasone 413
358 Stability study of DSP was performed using 100 mg L−1 removal 414
359 solutions in pure water, or AS taken from the WWTP 415
360 The efficiency of WWTP at Al-Quds University for the 416
installed at Al-Quds University. Samples at specific removal of DSP and dexamethasone was studied. The
361 time intervals (0–14 days) were collected from the 417
362 AS reservoir (site 1 in Figure 1) was separately spiked 418
stability solutions (maintained under continuous orbital with either DSP or dexamethasone at a concentration
363 419
364
shaking), filtered and analysed by HPLC. The degra- of 1.0 mg L−1 , which is an amount close to literature 420
dation by-products of DSP were investigated using findings.[8,11] Samples were taken from different collect-
365 liquid chromatography/Fourier-transform ion cyclotron 421
366 ing sites of WWTP as described in Section 2.2.2 and 422
resonance/mass spectrometry. Figure 1. Analytical results of water effluent from UF
367 423
368 system indicated that the efficiency of the UF process is 424
369 about 63–95% (sample nos 4 and 6, see also Figure 1 and 425
2.2.4. Micelle–clay complex preparation Table 1).[24,25] DSP was completely removed in the efflu-
370 426
The ODMTA MC complex was prepared by mixing a ent from GAC filter. However, it should be outlined that the
371 427
smectitic clay mineral (montmorillonite) with the cationic concentration of DSP (or dexamethasone) influent in the
372 428
surfactant ODTMA (as bromide salt) with a critical micelle treatment units was diminishing along their sequence. This
373 429
concentration value of 0.3 mM as described previously.[21] relationship reflected upon 100% removal by GAC filter,
374 430
375
The added surfactant was mostly in micellar form. The where influent water contained only 0.06 mg L−1 of DSP, 431
376
obtained complex by virtue of its positive charge and or 0.07 mg L−1 of dexamethasone, on average, after the pas- 432
hydrophobic region is capable of efficiently binding neutral sage through the UF filters. This finding made unnecessary
377 433
and negatively charged organic molecules.[21–25,28] the use of RO for any further purification. Nevertheless,
378 434
379 the advanced technology adopted in the WWTP of Al- 435
380 Quds University did not overcome a problem common to all 436
2.2.5. Batch adsorption experiments plants: the production of brine, in which a large portion of
381 437
382 Batch adsorption experiments were carried out on DSP at the contaminants ends up being concentrated there. For this 438
383 different concentrations. Experiments were performed in reason, different methods of water filtration and purification 439
384 250 mL Erlenmeyer flasks containing 200 mg of either MC should be experimented. 440
385 complex or FAC; 100 mL of DSP solutions having known 441
386 initial concentration was then introduced into each flask. 442
The flasks were shaken in an oscillating shaker for 3 hours 3.2. Stability of DSP in pure water and in sludge
387 443
388 at room temperature, and then the content of each flask was Literature survey on the stability of DSP indicates 444
389 centrifuged (10,000 g) for 5 min and filtered using 0.45-μm that the drug undergoes degradation in aqueous solu- 445
390 filters. The equilibrium concentrations of DSP were then tions buffered at various pH values, temperature, light 446
391 obtained by HPLC, using the conditions reported above. exposure and oxidative conditions.[29] Furthermore, 447
392 The retention time of DSP was 6 min. DSP cleaves into four major degradation products. 448
 Environmental Technology 5

449 Table 1. Removal of DSP and dexamethasone (hydrolysis product – HP) from wastewater by different treatment units in Al-Quds 505
450 WWTP; average values of three replicates. 506
451 Concentration of DSP and dexamethasone (HP) (mg L−1 ) 507
452 508
453 Means ± SD Remaining (%) 509
454 Sample description Sampling site as in Figure 1 DSP HP DSP HP 510
455 511
AS spiked amount 1 1.0 1.0
456 512
UF-HF Influent 2 0.83 ± 0.05 0.81 ± 0.02
457 Concentrates produced 3 0.46 ± 0.04 0.43 ± 0.04 513
458 Effluent 4 0.31 ± 0.03 0.24 ± 0.02 37.3 29.6 514
459 UF-SW Concentrates produced 5 0.19 ± 0.02 0.17 ± 0.02 515
460 Effluent 6 0.06 ± 0.03 0.07 ± 0.04 5.3 8.6 516
GAC effluent 7 b.l.d. b.l.d. ≈0.0 ≈0.0
461 517
462 b.l.d., below the limit of detection. 518
463 519
464 Pure Water (a) Wastewater (b)
520
465 521
5.0
466 522

Colour online, B/W in print

467 4.0
523
468 y = –0.0281x + 4.6190 524
469 R2 = 0.9981 525
3.0

Ln C(t)
470 526
y = –0.3299x + 4.6007
471 2.0 R2 = 0.9987
527
472 528
473 1.0 529
474 530
475 0.0 531
476 0 2 4 6 8 10 12 14 532
477 Time (days) 533
478 Figure 3. Kinetics of DSP degradation in pure water (plot a) 534
479 and activated sludge (plot b). Data are reported as natural log- 535
480 arithm of concentrations (C(t) ) vs. time. Initial concentration 536
481 (C(0) ) = 100 mg L−1 . Plotted values are the means of three repli- 537
Figure 2. Chromatogram showing the appearance of an intense cates; bars represent the standard deviations calculated for each
482 average value.
538
peak attributable to dexamethasone, the hydrolysis product of dex-
483 amethasone sodium phosphate risen after 2 weeks of incubation
539
484 in pure water. 540
485 541
486 to 2.1 days in the AS, where the concentration of the parent 542
487 They were identified as dexamethasone-21-oic acid, 17- molecule was found at the level of 1 mg L−1 after 2 weeks 543
488 oxodexamethasone, 6β-hydroxy dexamethasone and 16,17- of incubation. The degradation rate in the sludge medium 544
489 unsaturated dexamethasone.[30] was about 12-fold faster than in pure water. The accelerated 545
490 Figure 2 illustrates the HPLC chromatogram of DSP degradation can be attributed to bioactivity of the AS. 546
491 after 2 weeks of incubation in pure water at room tempera- Monitoring the derivative substances arising from the 547
492 ture (C(0) = 100 mg L−1 ). The peak at 6-min retention time degradation of DSP in the AS showed that the first 548
493 is characteristic of the acidic form of DSP, and the peak at degradation product, dexamethasone, underwent further 549
494 10.3-min can be attributed to its hydrolysis product dexam- degradation to other by-products as identified-by mass spec- 550
495 ethasone. The kinetic data of DSP hydrolysis in pure water trometrical analysis. Extracted ion chromatogram (XIC) of 551
496 are plotted in Figure 3 (plot a) as natural logarithm of DSP the 14-day biodegraded sample is shown in Figure 4. Using 552
497 concentration vs. time (days). The determination coefficient very selective XICs by FT-ICR/MS, generated with a tight 553
498 R2 of the first-order hydrolysis reaction was 0.9981, and the mass-to-charge ratio window of ±0.0010 units around each 554
499 kinetic constant was 3.25 10−7 s−1 . selected protonated molecule (i.e. [M + H]+ ± 1.0 mDa), 555
500 Similarly, a kinetic study on the stability of DSP was greatly reduced the signal complexity of the total ion current 556
501 conducted in the AS at room temperature. The determina- trace (data not shown) allowing to completely characterize 557
502 tion coefficient R2 in this case was 0.9987 (Figure 3, plot b), all degradation products. 558
503 and the kinetic constant was 3.80 × 10−6 s−1 . The degrada- In addition to dexamethasone, which was formed from 559
504 tion half-life was diminished from 24.7 days in pure water hydrolysis of DSP, seven major biodegradation products 560
 6 S. Sulaiman et al.

561 10.23 NL: 1.24E4 617

100
12.55 m/z= 409.20109-409.20309
562 50
618
Colour online, B/W in print

563 619
0 NL: 1.25E5
564 100
8.59 620
565 m/z= 313.17882-313.18082 621
50
566 622
567 0 NL: 9.08E3 623
8.59
100
568 m/z= 295.16826-295.17026 624
569 50 625
570 0 NL: 5.83E4 626
10.11
100
571 m/z= 389.19487-389.19687 627
572 50 628
573 0
9.68 NL: 1.91E6 629
574 100 630
m/z= 335.20070-335.20270
575 50 631
576 8.53 632
0 NL: 6.68E5
8.53
577 100 633
m/z= 333.18505-333.18705
578 50 634
579 11.09 635
0 NL: 2.38E5
10.48
580 100
m/z= 411.21674-411.21874
636
581 50 637
582 0
638
583 0 2 4 6 8 10 12 14 16 18 639
584 Time (min) 640
585 641
Figure 4. Extracted ion chromatograms (XICs) acquired by LC/ESI-FTICRMS in positive ion mode for the aqueous sample collected
586 after 2 weeks of biodegradation from the activated sludge spiked with 100 mg L−1 of DSP. The ions monitored are displayed in each trace 642
587 and correspond to the most abundant protonated moieties [M+H]+ , using a restricted window of ±0.0010 m/z unit centred around each 643
588 selected ion (Table S1 in Supplementary material). 644
589 645
590 were identified arising from dexamethasone biodegradation The FT-ICR infrared multiphoton dissociation MS/MS 646
591 at retention times 8.53 (3), 10.23 (4), 9.68 (5), 10.11 (6), spectrum, reported in Figure S1 (Supplementary material), 647
592 8.59 (7), 8.59 (8) and 10.48 (9) minutes. Based on the accu- shows that compound (8) gives a molecular peak at m/z 648
593 rate m/z values (Table S1, in Supplementary material) and 313 and three fragments with m/z 295 [M-H2 O + H]+ , 277 649
594 relevant literature,[30] we propose the following structures [M-2H2 O + H]+ and 267 [M-H2 O − CO + H]+ , due to the 650
595 for all degradation products evolved (Figure 5): loss of H2 O and CO. In Figure 7, the first pathway (A–B) 651
596 leads from compound (4) to compound (3) by the loss of 652
597 C20 H25 FO3 [17-oxodexamethasone] (3), 653
H2 O, formaldehyde and CO moieties, then to compound (8)
598 C22 H29 FO6 [6 -hydroxy dexamethasone] (4), 654
through the loss of hollow fibre (HF). The second pathway
599 C20 H27 FO3 [testosterone] (5), 655
(C–D) leads from compound (4) to compound (6) by the loss
600 C22 H28 O6 [3 ,4 -dihydroxy-10,13-dimethylspiro[1,2,6,7,8, 656
of HF molecule, and successively to compound (8) with the
601 9,12,14,15,16-deca hydro cyclo penta [a] phenanthrene- 657
loss of water, formaldehyde and CO groups.
602 17,5 -oxolane]-2 ,3,11-trione] (6), 658
To the best of our knowledge, no publication has
603 C20 H22 O2 [(8S,13S,14S,17S)-13-methyl-3-oxo-2,6,7,8,14, 659
appeared on biodegradation of DSP or dexamethasone in
604 15,16,17-octahydro-1H-cyclopenta [a] phenanthren-17-yl] 660
wastewater. However, there are some in vitro and in vivo
605 (7), 661
studies in rat and human livers on DSP metabolism to 17-
606 C20 H24 O3 [(8S,13S,14S,17R)-17-ethynyl-17-hydroxy-13- 662
oxodexamethasone and 6-hydroxy dexamethasone, which
607 methyl-1,2,6,7,8,14,15,16-octahydrocyclopenta[a]phenan- 663
are two of main derivative substances we report in Figure 5
608 thren-3-one] (8), 664
as number (3) and (4), and side chain cleaved metabolites
609 C22 H31 O6 F [6-Fluoro-11,14,17,21-tetrahydroxy-16-meth- 665
[30] having a structure different from derivatives identified
610 ylpregn-4-ene-3,20-dione (9). 666
in our work.
611 Figure 6 describes the suggested pathway by which 667
612 dexamethasone degrades to metabolites (4) and (9). The 668
613 hydroxyl group can attack two different positions on the 669
dexamethasone moiety. Figure 7 illustrates the proposed 3.3. Adsorption isotherms
614 670
615 pathways for the degradation of (4) to the other degradation The adsorption of DSP at several initial concentrations 671
616 products (3, 6, 7 and 8). on MC complex and activated charcoal was investigated. 672
 Environmental Technology 7

673 O
OH
729
HO Me O
674 OH
Me OH 730
675 Me Me 731
Me Me
676 732
677 733
F F
678 O
734
679 3 O 4 735
OH
680 O 736
OH Me OH OH
681 Me 737
OH OH
682 Me Me 738
Me
683 Me
739
684 740
F
685 741
O
686 O OH 742
5 6
687 743
H
688 Me OH H 744
Me
689 OH OH 745
Me
690 Me
Me Me 746
691 747
692 748
693 O
O
749
694 7 8 750
695 751
O
696 OH 752
697 OH
Me OH 753
698 Me
754
Me
699 755
700 756
F
701 757
O
702 758
OH
703 9 759
704 760
Figure 5. Chemical structures of dexamethasone biodegradation products. 17-Oxodexamethasone C20 H25 FO3 , exact MW
705 332.17822 (3); 6-hydroxy dexamethasone C22 H29 FO6 , exact MW 408.19427 (4); testosterone C20 H27 FO3 , exact MW 761
706 334.19387 (5); 3 , 4 -dihydroxy-10,13-dimethylspiro[1,2,6,7,8,9,12,14,15,16-deca hydro cyclo penta [a] phenanthrene-17, 762
707 5 -oxolane]-2 ,3,11-trione C22 H28 O6 , exact MW 388.18804 (6); [(8S,13S,14S,17S)-13-methyl-3-oxo-2,6,7,8,14,15,16, 763
708 17-octahydro-1H-clopenta[a]phenanthren-17-yl] acetate C20 H24 O3 , exact MW 312.17200 (7); (8S,13S,14S,17R)-17-ethynyl- 764
709 17-hydroxy-13-methyl-1,2,6,7,8,14,15,16-octahydrocyclopenta[a]phenanthren-3-one C20 H22 O2, exact MW 294.16143 (8); 765
[6-Fluoro-11,14,17, 21-tetrahydroxy-16-methylpregn-4-ene-3,20-dione C22 H31 O6 F, exact MW 410.20992 (9).
710 766
711 767
712 Equilibrium relationships between adsorbent and adsorbate values for MC complex are 652.1 mg g−1 and 2.795 L mg−1 , 768
713 can be described by Langmuir adsorption isotherm,[24,31– respectively, whereas the values for activated charcoal are 769
714 33] represented by the following equation: 103.4 mg g−1 and 0.184 L mg−1 , respectively. The Lang- 770
715 muir binding constant ‘k’ for the MC complex was about 771
716 Ce 1 Ce 15-fold greater compared with the activated charcoal, and 772
= + (1)
717 Qe (k Qmax ) Qmax the value of Qmax was nearly sixfold higher for the former. 773
718 The values of k and Qmax parameters suggest that the MC 774
719 where Ce (mg L−1 ) is the equilibrium concentration of the complex is a better adsorbent of DSP than the activated 775
720 drug in the solution, Qe (mg g−1 ) is the equilibrium mass of charcoal. 776
721 the adsorbed drug per gram of complex or activated char- 777
722 coal, k (L mg−1 ) is the Langmuir binding constant and Qmax 778
723 (mg g−1 ) is the maximum mass of drug removed per gram 779
of complex. 3.4. Modified clay adsorption
724 780
725 The data fitted well the Langmuir equation giving DSP solutions were passed through filters that included the 781
726 R2 = 0.9953 for activated charcoal and 0.9997 for the MC MC complex or activated charcoal mixed with excess sand 782
727 (Figure 8). Langmuir constants Qmax and k were deter- at 1:50 ratios (w/w). Results (Table 2) indicate a significant 783
728 mined from the slope and intercept in Figure 8. These advantage of the MC filter in removing DSP compared with 784
 8 S. Sulaiman et al.

785 O 841
786 P 842
O O Na
787 O 843
O
788 HO Me Na 844
OH
789 845
Me
790 Me 846
791 847
792 F 848
O
793 1 849
794 Hydrolysis 850
795 851
O OH
796 852
HO Me OH
797 853
798 Me Me 854
799 855
800 856
801 F 857
802 O 858
2
803 859
804 Hydroxlation & Hydroxlation 860
805 Reduction (a) 861
806 (b) 862
807 863
808 864
809 865
O OH
810 O OH 866
HO Me OH
811 Me OH 867
HO
812 Me Me 868
813 Me Me 869
814 870
F 4 C22H29FO6
815 C22H31FO6 871
F 9
816 O 872
O OH
817 OH 873
818 874
Figure 6. Proposed transformation pathway for the biodegradation of dexamethasone sodium phosphate (1).
819 875
820 876
821 the removal by activated charcoal. This finding was not sur- in contrast, a filter filled with the same weight of activated 877
822 prising, since parameters obtained for adsorption isotherms carbon and sand only partially removed these pollutants. 878
823 have clearly shown that the MC complex was more effi- In a recent paper, Karaman et al. [24] showed that MC 879
824 cient than the activated charcoal in adsorbing DSP from filters were more efficient towards the removal of diclofenac 880
825 water. potassium from wastewater than activated carbon. Morover, 881
826 Previous reported experiments demonstrated the advan- Khamis et al. [1] concluded that the incorporation of MC 882
827 tage of the MC filters in removing anionic and certain filters in sewage treatment systems with loose tertiary capa- 883
828 neutral pollutants.[21–23] bility can be a promising technology. More recently, Khalaf 884
829 Polubesova et al. [21] found a very efficient removal et al. [25] suggested that the integration of clay–micelle 885
830 from water of neutral and anionic herbicides by micelle– complex filters in existing WWTPs may be helpful for 886
831 clay complexes. In another study,[22] column filters filled improving the removal efficiency of recalcitrant residues 887
832 with a mixture of quartz sand and micelle–clay complex of non-steroid anti-inflammatory drugs. 888
833 provided a very efficient result for the retention of tetracy- In laboratory study, Qurie et al. [32] found that micelle– 889
834 cline and sulphonamide pharmaceuticals from wastewater. clay complex filters under continuous naproxen-spiked 890
835 Zadaka et al. [23] tested column filters with either a mix- water flowing are efficient in removing naproxen, suggest- 891
836 ture of quartz sand and organic micelle – montmorillonite or ing that the efficiency of the existing advanced WWTP 892
837 zeolite; both filters were capable of removing well ethylene could be improved by including filtration columns filled 893
838 dibromide, anionic pollutants as sulphosulphuron, imaza- with suitable sand/micelle–clay mixtures. 894
839 quin and sulfentrazone, and neutral compounds such as It can be argued that in addition to DSP residues 895
840 bromacil and chlorotoluron from aqueous environments; wastewater usually includes other recalcitrant organic 896
 Environmental Technology 9

897 m/z 409 953

898 C22H30FO6 + 954
899 4 –H2O 955
–HF –CH2O
900 A –CO
956
C
901 957
902 958
903 O 959
OH HO Me O
904 Me 960
OH OH
905 Me Me 961
906 Me Me 962
907 963
908 m/z 333 964
F
909 C20H25FO3 + 965
m/z 389 O
910 O OH C22H29O6 + 3 966
6
911 967
–H2O
912 D –CH2O B –HF 968
913 –CO 969
914 970
H
915 Me 971
OH OH
916 972
917 Me Me 973
918 974
919 m /z 313 975
920 C20H24O3 + 976
921 O 977
8
922 978
–H2O
923 979
924 H 980
Me OH
925 981
926 Me
982
Me
927 983
928 m/z 295 984
929 C20H22O2 + 985
930 986
O
931 7 987
932 988
Figure 7. Proposed transformation pathways for dexamethasone (4).
933 989
934 990
935 Activated Charcoal Micelle-clay 991
936 9.0 Table 2. Removal of DSP by filtration of 1 L of pure water 992
Colour online, B/W in print

937 8.0 y = 0.0097x + 0.0526 solutions (100, 10, 1.0, 0.01 mg L−1 ) through laboratory filters, 993
938 R2 = 0.9953 which included either MC or GAC mixed with excess sand at 994
7.0
939 1:50 (w/w) ratio; means of three replicates. 995
6.0
940 996
Ce/Qe

5.0 Initial concentration Column Average eluted

941 (mg L−1 ) typea concentration (mg L−1 ) ±SD 997
4.0
942 998
3.0 y = 0.0015x + 0.0005
943 100 MC b.l.d. – 999
2.0 R2 = 0.9997
944 100 GAC 64.3 1.2 1000
1.0 10 MC b.l.d. –
945 10 GAC 3.1 0.5 1001
946 0.0 1002
1.0 MC b.l.d. –
0 200 400 600 800
947 Ce (mg L–1)
1.0 GAC 0.17 0.08 1003
948 0.01 MC b.l.d. – 1004
949 Figure 8. Langmuir isotherms for the adsorption of DSP by 0.01 GAC b.l.d. – 1005
micelle–clay complex () and by activated charcoal (). Dosage
950 of adsorbent (0.2 g). Data reported are means of three replicates. a Flow rate, 2 mL min−1 ; temperature, 25◦ C; b.l.d., below the 1006
951 Bars represent standard deviations of means. detection limit of the analytical method used. 1007
952 1008
 10 S. Sulaiman et al.

1009 pollutants.[33–36] In such cases, GAC filters can be used as Estrogenic effects in fish in English rivers with evidence of 1065
1010 a first-stage tertiary process to remove the majority of neu- their causation. Pure Appl Chem. 1998;70:1795–1804. 1066
1011 tral pollutants, and additional MC filters can be adopted as [6] Johnson AC, Belfroid A, Di Corcia A. Estimating steroid 1067
estrogens inputs into activated sludge treatment works and
1012 the second stage to eliminate anionic pollutants, and neutral observations on their removal from the effluent. Sci Total 1068
1013 compounds not retained by GAC filters. Environ. 2000;256:163–173. 1069
1014 [7] Johnson AC, Sumpter JP. Removal of endocrine disrupting 1070
1015 chemicals in activated sludge treatment works. Environ Sci 1071
1016 4. Conclusions Technol. 2002;35:4697–4703. 1072
In this study, we determined the rates of degradation of [8] Ternes TA. Occurrence of drugs in German sewage treatment
1017 plants and rivers. Water Res. 1998;32:3245–3260. 1073
1018 DSP in pure water and in sludge. The degradation products, [9] Jones OAH, Voulvoulis N, Lester JN. Human pharmaceu- 1074
1019 which were identified by LC–MS and LC/MS/MS tech- ticals in wastewater treatment processes. Crit Rev Environ 1075
1020 niques, were found to include not only the already known Sci Technol. 2005;35:401–427. 1076
1021 metabolites 17-oxodexamethasone and 6 -hydroxy dexam- [10] Hirsch R, Ternes TA, Haberer K, Kratz KL. Determina- 1077
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1022 environment. Vom Wasser. 1996;87:263–274. 1078
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1025 technologies installed at the WWTP of Al-Quds University a case study. J Hazard Mater. 2005;122:195–204. 1081
1026 were effective for the complete removal of both DSP and [12] Ohlenbusch G, Kumke MU, Frimmel FH. Sorption of phe- 1082
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1027 micro extraction. Sci Total Environ. 2000;253:63–74. 1083
1028 The filtration performed using the mixture sand/MC [13] Goodman-Hilman A, Rall T, Nier A, Taylor P. The phar- 1084
1029 complex was able to remove and retain very high con- macological basis of therapeutics. New York: McGraw-Hill; 1085
1030 centrations of DSP from aqueous solutions. The large 1996. 1086
1031 effectiveness and removal capacity of the MC complex are [14] Schepers A, Pires Nuno MM, Eefting D, de Vries MR, van 1087
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1032 ment inhibits vein graft thickening in hypercholesterolemic 1088
1033 by the relatively large number of positively charged and ApoE3Leiden transgenic mice. J Vasc Surg. 2006;43: 1089
1034 hydrophobic sites of the MC complex based on ODTMA. 809–815. 1090
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