Journal of Water Process Enginering 48 2021) 102226 Contents lists available at ScienceDirect Journal of Water Process Engineering journal homepage: ww elsevier-comilocatelwpe Removal of a mixture of veterinary medicinal products by adsorption onto a Scenedesmus almeriensis microalgae-bacteria consortium Johanna Zambrano”, Pedro Antonio Garcia-Encina“", Félix Hernandez, Ana M. Botero-Coy “, Juan J. Jiménez*", Rubén Trusta-Mata *": 2 ma of Sune Pracs, Une of Valle De Magen 47011 Vlad Span = Deptt of Chana geri ond ental Thal Sea of nual Epc, Unerayof Vlad, Dr Merging), 4701 Vallat Spa se Bt 108 aoe 20> 162 Teaaeyloe rer] S340 aga” woe1, SEM iauge of (A) Scoedesmus abnerinssbacttia consortia, (B) rkcur of arbiois and () blamass exposed to ania ‘monitored during the whole operation process, remaining constant around 8.6 1 0.2, Samples were filtered immediately through 0.22 mn pore size nylon syringe filters Fisherbrand) and stored at 4 °C before ‘analysis of the aqueous phase antibiotics concentration. Experiments ‘were conducted in rpliate raf Wan Pres gang #82021) 10226 24. Analytical method Microalgae surface groups were identified by Fourier transform Infrared (FTIR) spectroscopy, using Bruker Tensor 27 spectrometer in the attenuated total reflectance (ATR) method. Morphological charac terization was carried out using a Hitachi FlexSEM 1000 scanning electron mieroseope (SEM). FTIR and SEM analysis were done at the Industral Testing Laboratory of Castilla y Led (LEICAL/WVa), located in Valladolid University (Spain). ‘The quantitative determination of elected annbioties was performed by liquid chromatography eonpled with aden: mass spectrometry (Lc MS/MS) with triple quadrupole (Waters Acqulty H-Class UPLC, equlp Ded with binary pump syste, interfaced to ciple quadrupole Xevo ‘TQ-STM mas spectrometer, with EST source (Waters Corp). The pro cedure wns based on those previously developed by Botero Coy et al. (19), employing direct infection of the (diluted) samples, without any pre-concentration step. In this work, a dilution x 100 (samples fortified ‘1000 and $00 ng/nil) oF dilution +10 (samples fortified at 100 and 20 ng/mL) with MIl-Q water was made in order to reduce matrix ‘complexity and to adjust the sample concentrations to the linear dy namic range ofthe clibration curve. Isorope-labelled internal standards (QUIS) were added to the four analytes under study (ciproflexacin-48, sulfamethoxazole 46, sulfadiazine-1306,cetracycline.d6) and were used for porential nati effects correction. Three MS/MS transitions were acquired foreach compound — one for quantification and the remaining nes for confirmation ofthe identity of the compound ¢Vable 2), The analytical procedure vas as follows: « 100 yi aliquot of the sample was mixed with 800 yi, Mill-Q water and a 100 wL mixture of four isotope labelled interval standards (118) at 2 yt (he samples fortified at 1000 and 500 ng/ml. were previously diluted 10 before applying the procedure by adding 900 pL Mill: water fo the 100 wl sample) Finally, 50 pl ofthe mixture were injected into the LC MS/MS. 25. Zero pot charge (2PC) 50 mi of Mill: water were taken in 100 ml. EHenmeyer flasks, adjusting the pH of each solution between 3 and 1, adding the appro. Driste amounts of 0.1 MU HCL and 0.1 M NaOH, 0.5 g of lyophilized biomass to each Erlenmeyer, and the final pH value was measured after 48 under stirring at room temperature. To ealeulate pH the values ofthe final pH are plotted vers the intial pH. The ple corresponds {o the point where the curve of final ptt vers nical pH cuts the graph diagonal 1201 26. Adsorption kinetics Pseudo firstorder (Eq. (1)) and pseudo second-order (Bq. (2) festations were used for the description of the adsorption kinetics. The linear form ofthe equations are expressed as (101 nea) = tna, byt @ a hea = where, qe (Hg/mg) and g (ig/mg) are the amounts of adsorbed antibi otis at equilibrium and at time t respectively, ky CQ") is the rate constant of pseudo fist order adsorption and ky (mage) is the rate coustant of pseudo second order adsorption, The q, values are calculated as fllows (Eq (3) L10} -6 @ where, C (18/1) is the antibiotic concentration in the inital solution and G, (pg/L) isthe antibiotic concentration in the solution at time , W (img) isthe amount of biosorbeat used in the experiment, and V (L)raf Wan Pres gang #82021) 10226 A San : g i sé A g ag 3 3 BP é sf LT ole : 3500 3000 2500 2000, 1500 1000 7 Sap) 2 & 9 5 i B Ge ie a 3 g 2 t 3 z g . 2500 3000 2500 2000, 1500 1000 Fig. 2. FTIR spectrum of S. alerts bacteria consortium before (hive ine) an afer (elie) (A) teracyline, (B) ciprofloxacin (C) sulfadiazine and (D) sl fanetoxszoleedsrpion. (For interpretation of the vefeences to color inthis gute legend, the vader i eered othe web version of this ate) corresponds to the volume of the solution. Therefore forthe pseudo fistorder equation, a plot of In (qe versus ¢ gives a straight line of slope ky and intereepts In qe. While, for the pseudo second-order equa Hon, a plot oft, versus gives a linear relationship, from which qe and ‘kg can be determined from the slope and inteseept of the plot [21]. 27. Adsorption isotherms ‘The Freundlich and Langmuir adsorption models were used for the mathematical description of dhe adsorption equilibria The Tinea form fof Langmuir isotherm (Eq. ()) and the Tinear form of Freunalie isotherm (Eq, (5)) are represented as follows (8,221 @ br ae= bak Moe © where, de (g/m) is the amount of adsorbed antibiotic per unit weight of biomass, C. (yg/L) isthe anubiotie concentration in the solution at equilibrium, Ke CL/ng) Is the Langmuir equilibrium constant, Qe (887 tg) isthe theoretical monolayer saturation eapacity, Ke (L/9g) Is the Freundlich constant, and n (ug/L) isthe adsorption intensity. Therefore, for Langmuir isrher, a plot of 1/qe Versus 1/Ce gives a straight line of slope 1/(gq, Ky aud intercepts 1/4q. While for Freundlich isotherm, « plo of log de versus fog Ge enables the constant Ke and exponent nto be determined (211,raf Wan Pres gang #82021) 10226 . | 8 (802) : \ : H MMe i 33 It fe oe | ta é 3 . D (sux) : : i Fig. 2 (contmued. : . ee. wal Fig. 3 Evaluation of nto polar charge (pM) for Scenedesmus almerenss bacterin consort, ‘3. Results and discussions 3.1, Surface morphology and functional groups of Scenedesmus falmeriensis bacteria consortium Biosorption may be accomplished by the functional groups and polymer assemblages present in microalgae and bacteria cell walls. The effectiveness ofthe adsorption process will depend significantly on the huydvophiliety,fanetionality and strettes ofthe biomass (ig. 14) and the aniibioces (Pig. 18). A Scenedesmus almerenss bacteria consortinm fan be an effective biosorbent for antibiotic removal as fe presents an especially tough cell wall with cellulose, algaenan and gl¥eoproteins (18,23). Scanning electron microscopy (SEM) was used to investigate the surface morphology of the Scenedesmus aleriensis bacteria con somtum (Pig. 14). Teean be observed tae te surface ofthe lyophilized biomass possessed pore structures, which makes dem ® good sorbent. SEM provides a qualitative evaluation ofthe cell wall structraf Wan Pres gang #82021) 10226 “Teuseyetine CratiaaNa0s 188 157 9.32 40,90,7,704005,9504030 [0] = 1058 40.30 - (sol HN, A 652 wat | ell wall was observed (morpliologieal changes of biomass surface) after ‘adsorption, which was confismed with FTIR spectroscopy (24 FTIR analyses were conducted ro identify the effect af the antibiotics ‘on the functional groups on the surface ofthe Scenedesius aimerenss bacteria consortium. The PTIR spectrums of the S. almerienss bacteria ‘consortium showed broad bands overs wavenumber range of 3600-800 ‘en (OH band (3200-3400 ent“), CH and CH stretching (2930 ‘em, aromatic conjugated C=0 and C=C bonds (1640 em"), NH. ending and CN stretching (1520 emt"), CH bending (1430 em, carboxylate ion stretching (1875 em), C—OH phenolics (1270 ‘env, C=O single bonds (1150 em), C—O stretching (1049 em, and C08, (875 em) ig. 2). These results showed » sinilar pater ‘as others previously reported for S.almerieasis (2), showing stretching ‘vibrations of the characteristic bands of polysaccharides and proteins. ‘The FTIR spectrums in Fig. 2of the S. alnerienss bacteria consortium, before anibiore adsorption are represented by a blue color wile after ‘ndsonption by @ red one. The strong spectrum of the S. almerienss bac teria consortium deereased after the incorporation of antbiotes into the ‘system. For TET (Fg. 2) peak modifications were observed at C=O and IN=H stretching, which ate related to proteins, suggesting that TET was bounded on the surface of the S. aleriensis bacteria consortium via Internetions with these functionsl groups. CIP (Fig. 28) showed sharp peak modifications at C=O and N—H stretching aswell aso the band ia the range of 3500-3000 em ?, corresponding tothe hydrogen bonds of ‘arboliydrates tl protelns. These results indicate tat lower peaks were ‘associated with CIP adsorption to biomass surface via these functional ‘groups. While SDZ (Fig. 2C) and SMX (Fig. 2D) showed important peak modifications at C=O and NH steetching, hydrogen bonds and {C—0=€ stretching (1200-1100 em") of polysaccharides suggest that "hese funetional groups were involved in SDZ and SMX adsorption. FTIR ‘results showed changes in ehiemical groups related to polysaecharides ‘and proteins, Proteins aze highly hydrophobic and can contribute t0 ‘organic pollutant adsorption (111 To determine the iaternetions ecween the antibioties and the ticroalgae, the zero-point charge for the S. anerienss-bacteria can Sortium was determined (Pig. 5), The zero-point charge (ZPC) is the plt for which the biomass surface is globally neutral. Consequently, the lectrostatie aration berween the biomass particles ad antiboties is tinimal. Below ZPC value, the microalgae-bacteria consortinm surface 's positively charged and exerts an electrostatic force towards the negatively charged antibiotics In contrast, beyond this value, the sur face is negatively charged and repels the anionic antibiotics (10,26) He forthe S. almerens-bacteria consortium ws found at pH 6.5. “The preset study was performed at pH 8, ad therefore the biomass was negatively charge ‘The pH ofthe solution is major and sensitive factor that will contol the biosorption of the antibiotics into the biomass. Aggregation, hy” Arophobicity, electrostatic attraction or repulsion of the nntibioties will be influenced by the pH. In addition, the physicochemical characters Ues ofthe antibiotics ~ lke che oetano-water partition coefficient (log Ke) atid the acid-base dissociation constant (pk,) of the antibiotics — (Isble 8) are important parameters which will directly affect bio sorption, The microalgae bacteria consortium could remove dhe antbi tics based on the lipophilic property ofthe antibiotics. The higher the log Kgs the higher the lipophilicity, Meanwhile, pk influences lip ophilicy, solubility, protein binding and permeability. The lower the Dy te greater he lipophilicity (27-29) “The four antibioties used in the present study have Low log Kops showing chat these antibiotics are hydrophilic and wil tend to be dis solved in the solution, However, all ofthe antibioties studied have more than one pK, values. This causes dificulty in determining the adsorption mechanism of # ¢ompound because it as diferent dissociated species (cationic, neural, or anion). Different eemical specis may present diferent properties in regards to water solubility, volatility, UV ab: sorption, and reactivity with chemical oxidants [29,30] The following are predictions of the different interaction mecha isms based on the pF of the solution, the anibioties pk, and the pHzpe ofthe microalgae-baceria consortia:raf Wan Pres gang #82021) 10226 = oe “ ce ger | on foams | 5 4 oy © yeviamec eat verte Concion i") Tae) Fig. 5. Kinetic analysis for pseudo Seca oider eaetio for anibloleemsoval Fig. 4. Antibiotic removal by bosorpsion at (A) 1000 yg L (8) 500 we *, by biowypion a (A) 1000 iL (50 L (©) 100 ws * a CD) 20 () 100 gL "and (D) 20 yg Lina concenuations Eos bas sepresent = nial eoncetatons itor Dus vepeseat + standavd stor of mea ‘Standard error of maa,‘Table 4 raf Wan Pres gang #82021) 10226 Kinetic parameters forthe bosorption of antibiotics by the Scenedesmus cmeinss bacteria consortium. ‘Compound GOB) Guay) alin) Pout Recorder model ‘Pade send der mode 5 kana) aba 5 Seow Gon tia) a Game tb > G! Suiadiioe 1000 oz tot O08 soos oss a6 or Seas aoe Sutamethoszale 10001000, : oe 8 . ae es : os oa 080 fant he $99 am anes 96 8) at pH 8, TET (pK < pH < pKa willbe in its neutral form and present hydrophoble incersetions with the biomass that will be negatively charged [29]. li) CIP pK, are in the ranges of 3.0-6.3 forthe carboxylic acid group and 8.7-10.6 for the nitrogen on the piperazinyl ring, showing that the acid will be dissociated at pH values higher than 6.3, and the nitrogen wil be protonated at pl values lower than 8.7. Ths, at pH 8, CIP will be mostly dissociated, both postvely and negatively charged, and its cations might enlance its sorption capacity on the negatively charged microalgse bacteria on: sortums through eleeteostatie ateaeton (91,52), |i sulfonamides pk, values are in the ranges of 1.8-2.1 and 56-66. ‘Therefore, in the pH range of 2.1-5,6, the compound wil be ints neutral form, witle at higher pH the compound will be pre dominantly anionic. At pH 8, SDZ and SMX (pH > pK) will be negatively charged whieh will ease an electrostatic repulsion ith negatively eharged microalgae (29) 3.3. Bioworpion Batch experiments containing the dead biomass (lyophilized algae bacteria consortium) under dark conditions help to understand to What extent the investigated VMP are eliminated from the solucon solely by biosorption, whieh would mean that they are nor being destroyed during the microalgae wastewater treatment process But are transferred to the biomass, having important implications forts posible subsequent use as biofertilizer of animal feed, After 96 h of operation, the antibiotic removal by biosoption at an inital VM concentration of 1000 pg/L was 75%6 TET, 4336 CIP and 1296 SDZ; SMX did not indicate ‘removal by biosorption (Pig. 1A). At an initial VMIP concentration of 500 g/L, removals of 62, 46, 36 and 21% were presented by TET, Cl 'SDZ and SMX (Fig. 48), respectively. At initial 100 yg/L, TET, CIP, SOZ ‘and SMX showed 80, 64, 26 and 17% of biosorption, respectively (ig. 4), Finally, atu initial concentration oF 20 ye/L, the removal percentages were 80% TET, 301% SDZ and 30% SMX; CIP was completely removed by biosorption after 24h (ig. 4D). Biosorption acts as an important mechanism for antibiotic removal, ‘especially at low concentrations. Among the three spiked levels highs temoval was observed for 20 jg/1. One of the reasons why this happened veas because there was @ limited amonnt of biomass, 1000 g/L (typical valle at which raceways operate) which could not adsorb large amounts of VMP. This quantity will be determined in the adsorp tion sothera tests in which we will find the adsorption capacity of each -YMP per unit mass of adsorbent at equilibrium. TET aud CIP presented a rapid decrease in their concentration in the fist 24h, while SDZ and SMX decrease gradually during the whole operation time. In general, ‘TET and CIP showed a better affinity (0 the microalgae-bactria con sortum, which may explain why at high antibiotic concentrations, TET and CIP use the available somption sites in mieroalgae and bacteria walls first, leaving few spaces for SDZ und SMX. Furthermore, SDZ and SMX showsed low removal percentages by biosdsorption as they are highly water soluble and under the current pH condition they presented elec trostatic repulsion with the negatively charged microalgee, which could explain he limited binding of sulfonamides co the algal ces [95]. The resilis obtained inthe present study are comparable with pre ‘ious smies on antibiotic removal by microalgae; for TET at a 2-mg/L nical concentration, de Godos etal. [34] using C vulgaris (44-355 mg/L “TSS) after 43 h observed 50-71% removal Likewise he present study, with & mixture of anibioties, obtained around 72% for the half of the concentration used by de Godes etal. at 43 h. The lower removal ob- tained by de Godos er al. might be due o the concentration of micro algae present in the solution. Similarly, for the 2 mg/L TET inital concentration, Norvll et al, [35] achieved 9756 TET renova after 14 using algae bacteria consortia (0.95 + 0.02 g/L TSS) from a HRAP. Honever, the present sudy obtained around 70% of TET removal for 1 ug/L nt 14 h, The higher removal obtained by Norvil er al. could be because they used just TET and not a mixture of diferent antibiotics; hence, the biomass surface will have mote free available sites for Diaz et al. (96), using an algre-bacteria consortia from an THRAP with an initial concentration of 2 mg/L CIP obsained 52.9% removal due to sorption after 111 h. Comparably, the present study sing # mixture of antibiotics with 1:mg/L of CI obtained around 43% removal after 96 h operation, This showed that biosorption is an Important mechanism in CIP removal, which goes slong with the con Clusions of Hom-Diaz etal. On the other land, Xie etal. [11] invest gated the use of 80 mig/L Chlamydomonas sp. to remove CIP and SDZ with an initial concentration of 10 mg/L After 9 days of operation, only 5.306 CIP and 0.5% SDZ removal was observed, This intial concentra ton of antibiotics wns exemsey high in relation to those that can be found habitually. In addition, the concentration of chlangdomonas sp. twas stull,wich wold ease active sites of the microalgae tobe rapidly extausted. The present study dl not use a concentration as high as Xie Cal (11), but dhe analysis of CIP and SDZ at different initial concen. trations shovs that sulfonamides have a lesser tendency toe adsorbed ‘han other antibiotic families, such as fluoroquinolones, and that at higher antibiotic concentratious sorption decreases, whic corroborates Xie et al. findings.SS Fig. 6 Adsorption isotherms of (A) TET, (B) IP, (C) SDZ and (D) SMX onto ‘Scenedesmus aleriensis mietonge bacteria ‘consoitivn (With a Confidence Interval of 95) Bal aud Acharya (91) using 2.0-10° cells/ml ofa groon algae, Nan nochlors sp, and an initial concentration of 10 pg/L SMX obtained 11% ‘of removal die Co sorption after 14 days operation. In contrast, the present study obtained a higher SMX removal of 31% with a highe raf Wan Pres gang #82021) 10226 Tables lsoherm constants of antibiois ‘Compound Langa moda Freundlich mods & =F & : two me me) » {nical concentration of 2 p/Lin just 4 days of operation. This could be de the use ofS, almerienss, wie showed the best afiity for SMX sorption. Likewise, Kiki etal. [57] investigated the biosorption of SMX sing H,plavais, .capricormumum, S. quadricauda and €. vulgar, After 40 days of operation, 0-1.81% and 0.37-3.35% removal were obtained for initial concenttatious of 20 and 100 pg/L respectively. Comparisons with these rests confirm that, almeriens has a better removal off clency by biosorption when treating water polluted with SMX. Thus, by employing a literature review én which the amounts of microalgae wsed im each study and their removal efficiencies of VMP were compared, i has been demonstrated the Importance of determining the correspon Ing adsonption isotheris of eae VP. Additionally, Scenedesnis almeriensis micromlgse-boeteria com sortiim eapacity to adsorb VMP can be compared with other organic materials. Zeng eta, [38] aehleved 50 to 80% biosorption from 20 mg/L (IP by using various concentrations of rice straw bioehar from 0.210 1.6 /1. Huang etal. {9} studied the biosorption of 10 mg/L CIP by using rabbit manure biochar, and they achieved removals of 76 10 97% ‘varying the amount of blachar used from 0.2 to 2 g/L. Wu etal. [40] observed 21 to 5% biosorption of 25 mg/L CIP by using Eneromorpha prolifera in concentrations from 0.5 to 2 g/L. Guoting Li etal. (1) ob tained 78.8% blosorpton of 20 mg/L TET by layered earbon particles from seanveed Sargassum sp. Asan etal. [42] prepared sv dust derived functionalized graphitic carbon and obteined removals around 90% for100 mig/L TET ane SMX. Pi etal [43] achieved 47 co 7036 of 0.4 to 1.8 mg/L SDZ biosorption by the utilization of extracelular polymeric substances extreted from Klebsiella sp. J 84, Kinetic analysis ‘The biosoxption kinete ofthe four aforementioned antibod wes investgeted sith pseudo fistorder and pseudo second-order kinetic tuodel (ig 5). The values ofthe specific eaton rates, ks and ko, were olvaine by liner regression ofthe experimental dat Table #). From the studied kinetic equations, +2 valies ofthe pseudo sscond order equation were closer to unity, andthe ealeulated adsorbed antibod at equlibrium were closer tothe experimental values when compared wilh the pseudo fistorder equation. The pseiio second-order rat Constant, ka, forthe removal of antbiois by the Seeds alner fends bacterin consortiums are 1.78-27.09 righ? for TET, 0:11-26.66 maig Hh fr CI, 0186-849 mary "for SO, and 1.93-11.98 mug for SMD. The ky rate constant increased ith the decrease i the inital anibiorie concentration, de tothe lined noua of biomass presen inthe slut, the eatin los down es the available sorption sits get occupied. The ky rte cons was higher for CHP: the ghee rate constant for CIP i key de to the log Koy of CIP (0.32) which is higher dhan dhat of TET (~1.37, DZ (~0.09) and Su (0489, indicating that CIP was more easly nésorbed. CIP was dssoc ae dis eaons enhanced is sorption eapacty on the negatively Charged micronlgae and bacteria through electrostatic ateaction (32) ‘These results denoted tht sorption of CIP CoS anerensis was easier and faster than thet of TET, SDZ ad SMX ‘As far as we know, there are fe publications about biosorpton ki netics on the S. alnerienss bacteria consortium fr dhe four ntiboresconsidered in the present study. From the bibliography available, Choi ‘et al. (7] used Spirulina sp. for biochar production and determined & ‘constant reaction kinetic of TET adsorption of 0.014 lr”, Likewise, for 'SMX, Kiki tal. [57] determined constant reaction kinetes of 2.08-10 05.8310-° busing A. pluvials,S.capricorautum, S. quadeauda and G vulgaris. similarly, Xieet al. [11], using Chlamydomonas sp. obtained ‘constant reaction rates of 1.8210 *h* for CIP and 1.01-10°? h* for ‘SDZ. Likewise, Hom Diaz et al. (36] got a7.3:10~* hr? CP removal rate ‘constant by using an algae-bacteria consortia from an HRAP. Xiong et (941 for dhe biosorption of CIP by Chlamydomonas meviana, obtained ‘ate constants ranging from 5,04 10-4 0 3.29:10-9h-*, The inerease in removal rate was du co the addition of sodium acetate to enhance CIP removal by eo:metabolis. tn ths ase, biosorption ante active biomass ‘an musk other removal processes that pare adsorption, These studies showed fist or psedo frst nte constants; thus, quantitative compar sons cannot be done with the values obtained in the preset study ‘Qualitatively, we can say thatthe present study obtained higher com Sant rates without te need of any addtional substance, The compart ‘sons ofthese results indicate thacadsorpton of antbiotes is faster when, 'S. lmeriense is used, confirming that it has @ better performance for ‘antibiotic emaval by blosorption 4S. Adsorption eotherms To compare the adsorptive capacity ofthe S. amerienssbactria consortium to TET, CIP, SDZ sd SMX, Freundlich and Langn ‘esorption models Were used (i. 0). The Freundlich isotherms asunie ‘emlilayer adsorption eda bse on interactions between adsorbed tuolecules and non-ieal adsorption on heterogeneous surfaces. Never theless, the Langnii isotherm are based upon an assumption of nite number of binding sites, constant energies of adsomption and no inter section between adsorbed species (8104221 tn tis work, the Lang tuodel presented higher correlation coefient for all the auibioes studied. The values of saturation capacity (qq) fom Langit sotherm (Heble 5) were 089, 052, 0.26 and 0.01 yg/mg for TET, CIP, SD2 and SMX, respectively. These results indicated, assuming’ a monolayer saturation, that che S-ameriensismeteria consortium had & beter af finiy for TET The values of saturation capacity obtained fom the Langm isotherm are comparable with the amounts of adsorbed ance at ‘sql ealeulated by the pseudo second order Kite suodel. For {he intl concentration of 1000 g/L, the gy ves for TET and CIP are close to the gy calenlated of 0.72 nnd 0.50 png, respectively. How. fever, the gy vale for SDZ is closer tothe. calealated at the iii ‘concentration of 500 g/L which Was 0.14 Ha/ing Fn, for SMX, the ‘4 value waste sana eq caleulated a he nit eoncenvaion of 20 pe ‘The ress are consistent with previous findings [7], whieh deer: ‘mined dat the Langu model presented «higher corelaton coef cent than the Freundlich for TEP removal by spintina sp. derived Diochar. The isotherm constant values obtained for Kj and gy ere 1.81-10-* Lig and 147.9 yp/mg, respectively (8). The current study obtained a higher Ky of 3.43:10-* 7p but a lower gy 0F 0.89 wy, probably due to high temperatures at which pyrolysis takes place to produce biochar which enhanced hydrophobicity ad the spi sur fnce aren of the mirongae. To dhe best of our knowledge, no oxber hors have published isotherm const fr CIP, SDZ aud SMI wing Ihicroalpnehacterin consort, so rte cnsparisons wih iterate «ould nat be done. 4. Conclusions Biosorption has been proven to be an important mechanism in the ‘removal of TET and GIP by microalgae based water treatment processes. For the frst time, the bosorption eapacity of the Scenedesmus amerenss microalgae bacterin consortium was analyzed sid proven to be highly raf Wan Pres gang #82021) 10226 bfficent in the removal of a mixture of four widely used VP. Fluo roquinolones aad tetraeyelines turned out to havea better lfniy to the S.almeriensis miroalgae bacteria consortium, showing high adsorption removal rates. Sulfonzmies presented limited biosomption inthe range OF 20 10 1000 pg/L. The Langmuir isotherm better described the adsorption process of tetracyline,ciprfloxacin, sulfadiazine and sul famethosazole, defining a monolayer adsorption with no interaction between adsorbed species. Further researc must focus on the other removal mechanisms of VMP during the microalgae wastewater treat ment process to find the best conditions to enhance mechanisms, whieh completely eliminate MP inorder to find a further use forthe harvested imieroalgn. Declaration of competing interest All the authors have declared no compet i terest Acknowledgements ‘This work vas supported by the Regional Government of Castilla y Leda (UIC 071, CLU 2017-09 and VAOSDGISD. The authors wish to ex press their gratitude to “Ministerio de Gieneia, tnnovsclin Unk ‘ersidados”(CTQ2017 84006 C31) ad the EL FEDER (CLL 2017-09 nd €TQ2017-84006-C3-1-R) for the Bascal support ofthis work “Thanks, are also iven to Jesus Medina from Valladolid University ato the Industrial Testing Laboratory of Casilla Lin fo thee suppoe with the FTIR and SEM analysis. Johann Zambrano wishes to thank the government of Castilla y Len for her Doctorate Contrat References {HK To Lh, Mies, Reino. TP Vn Bee. 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