‘Chemical Engineering Jor 428 (2022) 131161 Contents lists valable at ScienceDirect = Sat Chemical Engineering Journal ithe = ELSEVIER journal homepage: www elsevier.comilocatelce} ® Efficient removal of microplastics from wastewater by an “ot electrocoagulation process Maoeai shen’, Yaxing Zhang'**', Bydhah Almatrafi"!, Tong Hu’, Chengyun Zhou", Biao Song'”’, Zhuotong Zeng” , Guangming Zeng” 2 igrmen of Dorms, Stcon Kegve Hoel Coal Sah Onverty, chagiha 10011, PR China = ali of nemo cnc nd ging Han ner en Ne ahr of iol aig and Palin Conte (Ma Urey), Miary of banca Chane #1082, PR Cine “Comer of aro clic Reena ery nd Pane Stns Center ofl Desa Techly, Dearne’ of Mechel Semen arity of Brome ROD, Re Ae Cowal, Joah 2156, Sed Araie ‘Wit the gradual increase of mleroplastes nthe water envionment, is iperative ro understand the removal ‘arate of miewplasties in the eaten teatment proces. Electocoagulaton (EC) san effective wate tueatmeat technology. The purpose of this study sto investigate the removal performance, mechanism ane influencing factors of microplates in wastewater teatment by EC. The lnpacts of wastewater prope, ‘melding nil pH, eleelyteconcenctio, applied voltage density, anode materials, mlvopastie ype a Injtoplastie concentrations, onthe removal eeeney of nicrplsties by BC wete systematically investigated ‘The findings showed that aluninimnanode was beter than ton anode in the removal of croplastc, md he removal rate of was above 80% in all experiment, which indieates that aluminum anode EC is an effective ‘hethod ro rentove microplates ia wastewater, The removal tate of for mltoplastles by ean reach re than 5296 in the range of pH 3-10, ad the best removal ate Was 93.285 for PE, 91.75 for PMMA, 98.2% fr CA ane 98.4% fr PP at pl 7.2, The removal efficiency of ibe microplate by EC is beter thn that of granule ‘njropastis. The mlcoplstic removal efficiency Increased with the increase of eleeuolyte conceatation and applied voltage density. Addionally, miopasis undergo flocculation and ehatge neutralization a the sane ‘ime duvng EC. The econonieevalation ofthe actor operation ost showed thatthe opine EC veseton ‘wontons wee: 0.09 M of electoyte concentration, pH 7.2, 10 V of applied voltage density and Al anode. Further research sould fous onthe posible eactor design ad improvement to optimize the proces and elie ‘he veplcation and transfer from te laboratory tothe sewage teataent plat 1. Introduetion environment and harm to human health (6-9). tn particular, because of its light density and small volume, micropastics ate easy tobe intake by ‘Nowadays, microplaste pollution has atracted more attention fom, the public, and has evolved into a global enviroamental problem (1-3) Evidence has shown that microplasties nay be stable in the aquatic ‘environment for thousands of years due o their ehemical stability [1.10 recent years, microplatics, considered as an emergent pollutant, have ‘cused serious economic loses in minrine ecosystem [| Because ofthe large specific surface area, persistence and Muidity, meropkastes are ‘easier to adsorb organic ciemical pollutants, heavy metals and harmful Intern, resulting in the increasing impact of miroplastes on the water faguatic organisms after entering the water body, resulting in acestinal abrasion and blockage [7,10]. The toxic chemicals attached 10 the plastie particles lso have great harms to aquatic organisms, and even tually pass (© human through the food chain, causing serious health problems. In view of the increasingly serious polhtion of plastics and micro plastis inthe world, governments have taken measures t reduce the etry of plastic produets into the environment (11). The munieipal wastewater rennet plant has been proved to bea major contributor of| * Coxresponding aubors at Depatmet of Deumatology, Second Xiangya Hospital, Ceatrl Sout Univesity, Changsha #10011, PR China mall adareser: 2engauocougcesu eden (2. Zeng) 2g. ca (6. Zeng) "hese authors connie equally to this ae. spa /do.org/10.2016 ee, 2021.131161, Availabe online 6 July 2021 1385, 8947/© 2001 kevier BY. All ight eservedricroplastics in the environment [12-14]. Although most of the ‘wastewater treatment plants have effectively removed the mieroplastics, ‘he municipal wastewater treatment plat is still an important source of ieroplasties in dhe environment [15]. In the process of land-based Input, a large number of plastic particles (such as plastic beads in daily chemical products, bers in laundry wastewater, car tire wear debris and other fragmented plastic waste) enter into the sewage pipe network, and then are treated by the sewage treatment plant and dis ‘charged into the environmental waterbody, and finally into the sen. At present, mieroplastes have not been inehided in the tentment seope of ‘sewage teatmient plants, and the research on the treatment efficiency ‘nd discharge of microplates in the existing process stil in the initia ‘stage Althoigh most ofthe miroplastes (90%) can be removed inthe sewage treatment plant according 10 the exstin sonie mieroplastes can sil bypass the sewage treatment plant snd enter the water environment with the wastewater [16], This obviously needs innovative, cheap and energy-saving solution, which can replace the existing three stage treatment process to solve the removal of mieto plastics in sewage, Electrochemical technology, eleetrocoagulation, provides a cheap tiree-stage wastewater treatment process, which does not rely on the chemicals or microorganisms wed in general chemical coagulation and traditional activated sludge process (1/|. Electro ‘coagulation is n complex process in which metal eleetrodes produce ‘ations tinder the ation of lecre Feld, The benefits of electrochensicel processes include environmental compatibility, low capital cost, energy efficiency, sludge minimization, ease of automation and cost effectiveness, and have been used to reaiove other pollutants from water [18,19] There are three consecutive stages fom the generation of fons co the formation of floes: (1) under the action of electre Feld, metal cations are ‘separated from anode to form “micro coagulant” (2) they are combined with suspended particles in water and sink together by colliding floes; and 3) coagulant fons a sludge layer for retaining suspended solid particles, The research on the removal of microplsties in wastewater by ‘lectrocongulation is still in its infaney. Perren, Wojtasik and Cai [17] studied the removal of microplastics from simulated wastewater by clectrocongulation with Al anode, and the effects of pH value, current ‘density and conductivity on the reovalefiiency of microplastes were studied, The rests show that the removal effiseney of microplates in ‘water by electrocoagulation was above 90%, especially 99.24% under neutral condition. However, the removal performance of microplasties by eleerocoagulation needs to be further optimized sn improved. Anode materials, types and shapes of mieroplasties, and the concentra Hon of microplates in wastewater all affect the removal of micro Plastis by electrocoagulation process In this pape, the feasibility of removing different types and shapes of inicroplasties in wastewater by eleetrocoagulation technology’ was sys temacieally explored. Two granular nuicroplasties (polyethylene, PE; polymethylmethacrylae, PMMA) and two fibrous mieroplastics (cell lose acetate (CA) from elgaredte butts; PP from disposable surgical asks) were chosen in this study due to their large proportion in sewage. ‘The addition of eatonie surfactane can not only increase the water sol ubilty of micreplasies, bat also increase the negative charge on the surface of aicroplastics. The effects of intial pH value of infiwent, electrolyte concentration (NasS0.), applied voltage intensity, anode material (Al and Fe), and type, shape and concentration of microplastics ‘nthe removal of mieroplastis by electrocongulation were studied. The feasible operation parameters of electroconguiation technology in ‘wastewater treatment were put forward according to the removal rate ‘and energy consumption, The application prospect of this method inthe thee stage treatment system of sewage treatnient plant was evaluated, which provides a powerful support forthe transfer and replietion front theory to practice. Chel Engen seul 4282022) 121163 2. Materials and methods 2.1, Materials and regents Two granular —microplasties (polyethylene, PE; poly: rethyimethacrylate, PMMA) and two fibrous microplastics (cellulose acetate (CA) from cigarette butts; PP from disposable surgical masks) were chosen in this study. PE and PMMA are wo common plastics in the sity life and obtained fromAleddin Chemie! Company (Shanghai, Ching). Evidence has shown that more dan 0.28 million tons of microplasti fibers are entering the aquatic environment from cigarette butts. Comparing this value with known sources of microplastie bers from textile and laundries, Ics expected fo release about 0.28 millon {ons of meroplasce fibers iro the aquatic environment each year (20) “The popilarity of COVID-19 has greatly incrensed the consumption of disposable masks, and has also increased ts chances of entering the ‘uviroument. Its estimated that there are about 129 billion masks used every month inthe world during COVID-19, most of which are dispos able masks made using microplastie flrs. A flly aged mask could release several billions of microplastic fibers into the aquatic environ: rent once these fragile fragnients enter the water widhout reservation 21}, Cigarette butts were collected from the environment, and masks were placed on the roof for two months of weathering treatment to obtain fiber mieroplastes (21). The masks are placed in a transparent sass caver to prevent the interference of other environmental plltants ‘nd the environmental pollution caused by weathered PP fiber. After ‘ovo mionths of natura weathering, the materials were carefully recy led. Two kinds of anode materials, aluminum (AD and iron (Fe), were obtained feom the Aladdin Chemical Company (Shanghai, China). Anionic surfactant sodium dodecyl benzenesulfonate (SDBS) seas pur chased from the Aldrich (USA) and aahydrons sodium sulfate (NasS04), nitic acid (H,S0.) and sodium hydroxide (NaOH) were obtained from the Alnddin Chemical Company (Shanghai, Ching). The water used in the experiments was ultrapure water extracted by MiIl-Q pure water sechanist, 22. Preparation of microplastic solution 1m order to Detter understand the inpactof wastewater properties, wastewater sinltor generates sinlated domestic wastewter cond tions while alloing fl contol variables. videuce has shown that the patil sizeof microplnstes fond in wastewater was grenter than SO jm [15]. In View ofthe high concentration of acroplstics in waste water with smaller parce, the representative mieroplasies in gran ar and fibrous form were enpatclly studied, which represen the greatest possibility of esceing fro the meatment process such Alocewlaton, coaglation nd sand Bltraton, The averige parle sizes of PIMA and PE granular meroplasties were measured to Be 6:3 um and 286.7 ym, espectively, while those of CA and PP fibrous mieeoplasties were bout 2m (i. 51. The concentration of miroplasis used ia this sty was controlled at 0.05, 0.1, 02, 0.5, 08 and 1g Ly respectively. PE micropastes are hydrophobi, so wo ensue the dh tulcospheres are completly dispersed in water, 20 nxp L-! of SDBS soufactant was added tothe solution, The surfactant ea sinulate the average surfactant concentration of domestic sewage sd help the Injeroplastieso form a uniform stspension (22) This concentation did nut necessary represent the concentration oF microplates in eal sewage and effuent, but it had dictions effect 2.3. Miropastc removal experiments (One liter of uniform suspension of microplastics with diferent com centeation was used for each experiment, and the experiment was eat ied out immediately after preparation. During the reaction, the Al electrode (4 em x 6 em) or Fe electrode (4 em % 6 em) was used as node, Cu electrode as cathode, thickness of 0.1 em, inserted into thelectrolytic cell as anode, and the plate spacing was 2 em (Fis. 52) hydrous Naz$Oq was added co the solution as an electrolyte, aad then, ‘voltage was applied to conduc the electrocoagulation experiment, To ‘explore the effect of diferent curren intensity onthe elecrocoagulation process, the concentraton af NayS0, was controlled at 0.01, 0.02, 0.05 ‘and 0.1 M, respectively. The effect of applied voltage density on microplastic removal was performed under the conditions of §V, 10 V ‘and 15 V. The sampling ime was 1, 2,3, 4,5, and 6 h. The initial pH ‘valine (3-10) of simulated wastewater was adsted by adding H-S0, (1 IM) oF NaOH (1 ND solution to study its effect onthe removal of micro lastis by eleetrocongulation process. With the development of elec twocougulation, the wastewater solution becanue more turbid which is ‘due to the formation of polymer floes. All the experiments were caved ‘out at room temperature with magnetic stirring speed of 150 rpms. ‘These floes were relatively easy to disperse in the whole container, and sone beads can be seen attached to the flocs. All the solutions cas, effectively participate in the electrocongulation reaction, After the ‘lectrocongilation experiment, the solution was evenly sired with & ‘glass rod, and then te beaker was placed on a clean and closed oper faving platform and allied o settle for 16 h (7). All experiments vere repeated chree ces, and all glass instruments were cleaned with ul- trapure water and alcobol three times before use. After each test, the reactor vessel was washed with ultapnre water and ultrasonic assis tance, und the electrode was Soaked in 1M H,S0, solution for 30 mi. ‘This isto remove mos of the oxide layer formed during the experiment, 80 as (© prevent electtode passivation from affecting the removal cfciency. 24, Determination After seting for 16h, the shidge blanket formed sunk into the bottom ofthe reactor, teking aay most ofthe ralroplasies. Compared ‘withthe original sample, che remaining liquid volume was significantly clearer. The removal efficiency of microplastis inthe process of ele trocoagulation was determined after exch experimental operation. Briefly, the supematant after setding was poured into anew clean glass beaker. The sludge was centrifuged at 3000 rpm for 10 mins at room Temperature, and the supernatant was collected, All supematants collected from each sample were filtered by 0.45 ym. microporous Iembrane, and 1 M HS0s solution was added during che filtration co prevent flaes carried on the surface of microplastis from blocking the membrane. Then the filter membrane was dried at 40°C for 24b, and the mass of microplastics ofthe dried sample was measured by calc lating the mass of each filter membrane before and after filtration. During the tst,chree parallel samples were taken at a ti the average valies of three samples were recorded. The toal removal eff ‘ieney of microplastis in the eleetrocoagulation process at each time Point was calculated by the following formula 100% o where Is the removal efficiency of miroplastes during the electeo ‘congiation (96); mf the mass oF mieroplasties inthe sokation ac the beginning of electrocoagulation process (mig); tm is the mass of microplastis in che supernatant after electrocoagulation process (mg). The centrifuged sludge was further observed by metallographic mit ‘roscope snd seanning electron microscope to investigate the removal mechanisms. The concentrations of Fe** and AI in the final effluent ‘were also measired, 2.8. Qualiy assurance and quality contol Some quality assurance and quality control measures were used ‘during the experiment. All the experinienters wore cotton clothes inthe process ofthe experiment. Al solvents were analyte grade (>95%5), Chel Engen seul 4282022) 121163 and all glassware were pre-leaned with 3096 ethanol solution, thor oughly rinsed with ultrapure water, then heat teated at 400 °C to remove organic impurities. By avoiding the use of any plastic equipment rnd using only elesmed glassware and metal items, the potential sources OF mieroplastic contamination were minimized. All filters have been cletned with ultrapure water before use to reduce the external micro plastic pollution and its own microplastic pollution. During the expet- tment, tie number of people in te laboratory was controlled. All filation processes are earied ont in 8 clean and enclosed operating platform, 8. Results 3.1. Variable study on nlcropasic removal S11. Bffect of anode mateiat 1m all the studies in this research, a large number of different inieroplasties was removed by the electracoagulation process, and the highest removal efficiency was measured to be >959%-100% statistical alysis indicated that the concentration of different microplastis in treated samples was always significantly lower than that in unreated control samples at each sampling time (p< 0.01). Different electrode materials have diferent electrochemical characteristic, so it is eruc to choose suitable electrode materials for improving the efficiency of electrocosgulation. The impact of anode materials on microplastic removal was thoroughly explored by using Al electrode and Pe elec trode. The experimental conditions were as follows: the concentration of four mieroplastes (PE, PMMA, CA and PP) was 0.5 g L-, the concen: tration of electrolyte (Na504) was 0.05 Mf, the pH of solution was not adjusted (pH = 7.2), and the applied voltage density was 10 V, respec Lively. ig 1 illustrated the effet of Al and Fe electode on microplastic removal during electrocoagulation. It can be clearly seen that in the process of eleetrocoagulation, microplstic removal efficiency of Al as ‘anode material was significant better than that of Fe as anode material. ‘The flocs produced by Fe electrode have dense precipitation and fast sedimentation, wile the flocs produced by Al electrode have fast speed, colorless degree and strong adsorption capacity. With the incresse of reaction time and fle concentration in the solntion, the removal rate of| mieroplasies was alo increasing, When the reaction time continued for 4b, the removal rate was basically unchanged (Pig. 1). The finally removal efficiency was 93.2% (Al) and 71.6% (Fe) for PE, 91.7% (Al) tnd 58.6% (Fe) for PMMA, 98.2% (AD and 85.49% (Re) Tor CA, and 98.496 (AD and 82.70 (Fe) for PP fiber, respectively, which was similar to the results of previous stidy (17) For granular microplastics, the removal rate of PE was higher than that of PMMA, The particle size of PE microplastic (286.7 um) was larger than that of PMMA (6.3 ym), which made i easier to be trapped when the floes produced by electrode sunk and avoided escaping froin the gap between floes. This phenomenon was more common in the electro: coagulation test with Fe as anode, because it was ficult for the sama size ofthe hydroxides to capture more PMMA microplastics ina large range. This also made thatthe removal efficiency of grannlar micro: pasties by electrogulation with Al anode was beter than tha of with Fe anode (Fig. S4-S7) Fr ibrons microplastics, the removal rate during electrocoagulation was obviously higher chan that of granular micro plastics (Fig. 1. t was because that the particle size of the two fiber Injeroplasties (CA and PP) in the experiment eas signifieanty larger than that of granular mieroplasties PE and PMMA) (Fg. 51). wd tion, the density (1) ofthe two fiber microplastics was also ane of the factors affecting the renioval rate. The removal efficiency of fiber tiicroplastics by electrocoagulation with Al electrode was more than ‘986 and 8296 with Fe. The findings showed tht electrocoagulstion with Al electrode had better removal effect on mleroplasties, and micro: plastis with larger particle size and density were easier tobe removed.Chel Engen seul 4282022) 121163 7 Ps a a ie ie fo aa] o. a i the 7 He =». =» Te ee =. * co ey q q i ie fa an| o. ea : ne ; — % 1 3 : 4 6 % 1 2 3 4 s 6 Tees ime Fig 1. Efe of Al and Fe electrode on removal of microplates rng electocongulaton. 12, Effect of applied electrolyte concentration Electrolyte concentration is a decisive parameter in electrochemical water treatment technology, which nor only has signifesnt impact on the renetion effect, but also has a eric impact on electric energy ‘consumption and operation costs, The impact of electrolyte concentra ton on microplnstic removal by electrocongulation process was thor ‘oughly studied by experiments under the conditions of 0.01 M, 0.02 M, 0.05 M and 0.1 M Na,S0,, The other experimental conditions were as follows: the concentration of four microplasies (PE, PMMA, CA and PP) Was 0.5 gL the pH of solution was noc adjusted (pt = 7.2), nd the applied voltage density was 10 V, respectively. Fig. 2 showed the effect ‘of diferent applied electrolyte concentration on microplastic during ‘lectrocongulation. As shovin in Fig. 2, with the increase of electrolyte ‘concentration, the removal rate of mietoplastiesinereased significantly. In the same electrolysis time, with the increase of electrolyte concen tration, the amount of Al°* and Fe” dissolved ont increased, and the ceffetive Al and Fe species produced increased, thereby increasing the aicroplastic removal efficiency. The removal rate was 85.496, 49.7%, 56.39% rnd 72.1% for PE, $9.43, 48.936, 53.2% and 68.4% for PMMA, 51.2%, 50.7%, 66.0% and 70.486 for CA, and 52.2%, 60.19, 68.59% and 70,80 for BP withthe electrolyte concentration of 0.01 M, 0.02 M, 0.05 Mand 0.1 M, respectively after 1 eleetrocoagutation with Al anode. ‘Whea the renetion time was extended to 6h, these removal efficiencies increased to 64.2%, 76,506, 93.2% and 94.196 for PE, 72.4%, 81.29%, ‘91.7% aud 95.7% for PMA, 88.23, 96.356, 98.2% and 98.79 for CA, ‘and 89.7%, 94.0%, 98.4% and 99.296 for PP with the eleetrolyte con ‘centration of 0.01 M, 0.02 M, 0.05 M and 0.1 M, respectively. Adal onal, the microplastic removal efficiencies also inereased with the Increase of electrolyte concentration wit Fe anode (Fs. 2) ‘The inipac of electrolyte concentration on the cost and operability of lectrocongilation process was also attalyzed, The current findings demonstrated that when the electrolyte concentration inereased ftom (0.05 stc00.1 M, the removal effect of microplasties was not significantly enhanced (His. 84-57). However, the floes produced in the reaction process obvionsly increased and the electrode was seriously damaged. In addition, dhe roslts showed that the average eurrent density was about 850 MIA, 600 mA, 1.52 A and 2.56 A for electrolyte concentration of 1.01, 0.62, 0,05 and 0.1 Mf, respectively with Al anode, respectively. The suergyconsuinption analysis implied that energy consuayption was 91.2 Kiwi m-? and 153.6 Ki mi? after 6 lat 0.03 Mand 0.1 M, respec tively. The consumption of electrolyte in the process of eleteo coagulation eannot be ignored. To ensure dhe stability oF the above blectrocoagulation, the minimam operating cost of miroplastc removal was 7.1 kg m™° NagS0, (0,08 MD, Consequently, tis necessary to comprehensively consider the microplastic removal effect and the en ‘ergy consumption ofeleetrode inthe aerual operation process (17,23) SS. Bifet of inital pH ‘he initial pH is also the main factor Co determine the treatment efficiency, which can be used for the removal of feed water turbidity in theeleetracoagulntion process. In this study, che experiment was carried ut in the range of intial pH value of 3-10 ro investigate its effect on ticroplastic removal efficiency and the other experimental conditions were as follows: the concentration of four microplastics (PE, PMMA, CA td PP) was 05 gL, the concentration of electrolyte (Naa604) Was 1.05 M, and the applied voltage density was 10 V, respectively. ig. 9 ilustrated the impaet of inital pH on microplastic removal during electrocosgulation over time. The Findings showed that microplastics in allpH ranges were successully removed, ad the fal removal rate was ‘more than 80%, implying that electrocongulation with AL anode was stable for mlcroplastierenioval fom wastewster witha ede range of DH value. The pH applicability of electrocoaguiation process meant that it can be effectively used in almost all ordinary domestic wastewater containing mleroplasties without adding more chemicals tous theRemora etn 4) Remora eine 6) Removal eens) Chel Engen seul 4282022) 121163 Rena eine 0) Rena eine 0) Rena fines) : Fig. 2. fect of ferent applied eee concenition DH value of wastewater, because the pH value of munteipal wastewater Is usually 69.2 (29) The final removal rate of each microplastic at pk 3 ‘and pH 10 was lower than that of pl 5 and pH 7.2 (ig. 3). When the pH ‘value of initial water was 3, loc formation can hardly be observed in the process of al eletroe reaction in short time, beesuse the pH of AI at 2 i =m i . oor on removal of mieropastis ding eletocagulation, the beginning of precipitation was higher, and dhere was litle OH the solution a this ime, floc formation was not conducive. For Fe anode system, loc formation can be seea almost immediately die to the low ntil precipitation pH of Fe”. These same experimental phenon Ihave also been reported in other studies (17.25). With the inerease of pH2 PPA PMMA-AI A CALAI— PPA Va Removal eficeney (%) Initial pit —ePe-Fe—* PMMAFe 4 Cre Pre i Removal eficeney(%) ty ee Initia pit Fig. 3. Effect of intl pH on leeuceoagulatin, removal of microplates during value of water, the floes formed in the reaction gradually increase, ‘which vas more conducive to the formation of AI(OH)s floes and Improved the removal rae of various microplastis. When the pH value fof water was 10, the removal efficiency of microplastics showed a downward tend, which was due to the amphoterie nature of alumni hydroxide, When the initial pH was 7.2, dhe Binal removal rate was 193.2% for PE, 91.7% for PMMA, 98.2% for CA and 98.4% for PP, respectively, and the pH value of simulated wastewater was similar co that of real municipal sewage. In addition, the zeta potential of four Ijeroplasties used inthis study eas shown fn Fig. $8. Under neutral ‘conditions, all the microplastis are negatively charged, which is more conducive to combine with the positively charged flocs to remove the iicroplastes from the water. The findings suggested that neutral pH ‘value was expected to provide better removal effet of mieroplastics in real sewage treatment because It was conducive to the produetion of| ‘congulants at neutral pH value during electrocosgulation. S14. Effect of applied voltage intensity Applied voltage density is a key parameter in the application of constant voliage electrocoagulaton, because itis an operating parant ‘eter, which can be directly controled by DG power supply with different test voltage strength. The effect of applied voltage density on micro plastic removal ves performed under the conditions of 5 V, 10 V and 15 Y, respectively, and the other experimental conditions were as follows the concentration of four microplasies (PE, PMMA, CA and PP) was 0.5 Chel Engen seul 4282022) 121163 1-4, the pH of solution was not adjusted (pH = 7.2), and the con- centration of electrolyte (N#gS04) was 0.05 M. Pig.) showed the removal effect of each microplastic over time under diferent applied voltage density by electrocorgulation. The removal race was 34.9%, 5.39% and 64.5% for PE, 29.68, 53.296 and 61.89% for PMMA, 42.69%, (66.696 and 71.296 for CA, and 44.436, 68.8% and 73.8% for PP with the applied voltage density of 5 V, 10 V and 15 Y, respectively, after 1 electrocoagulation with Al anode. When the reaction time was extended to 4h, hese removal efficiencies increase to 62.4%, 92.9% and 95.8% for PE, 58.65, 88.6% and 94.59 for PMBIA, 76.3%, 94.5% and 98.6% for CA, and 78.5%, 95.8% and 97.69% for PP with the applied voltage density 5 V, 10 Vand 15 V, respectively. However, at prolonged time of 6 hi these efficiencies have not increased significantly (Fig. 4). Cleary, flocculation and precipitation seemed to be the main mech nisms for microplastie removal when exees floes have produced daring electrocoagulation. This showed thar the increase of voltage (rom 10 to 15 V) aud metal ions would not lead to the increase of microplastic removal in the range of studied voltage density. The dominant tine of coagulant exeess and flocenlation mechanism seemed to be within 4, because the voltage density seems to have a more important effet on the removal of mieroplasties during this period. As shown in Pig. 4, the sradient of the removal efficiency line decreased after 4 h. The findings Suggested that compared with the precipitation afer 4h, the excess floes have been produced when the reactor ran for more than 4, whieh has litte impact of the microplastic removal eficiency. At the same time, the long-term operation of the eleetrocongulation device would inerease the sludge in che system, and increase the consumption of electrode and electric energy [17]. Additionally, based on these results, 1¢ was concluded that che inerease of voltage intensity would inerease the removal efficiency of microplasics. However, when voltage inreased to certain intensity, voltage density did not affect che removal efficiency of microplastics. Therefore, operation under appropriate voltage in tensity ean not only improve the removal efficiency of microplates, but also save energy consumption. The start time of exces sludge prod tion in the reaction system would depend on the conditions of the reactor, especialy the current density, and can be used co determine the optimal operation time ofthe reactor concerned. 2.1.8. sffect of meropastic concentration ‘The concenteaion of mieroplastcs in wastewater is also an impor tant factor affecting tae removal efficiency of electrocoagulation. Ev ‘dence has shown that the occurrence of microplates in che influent ‘varied from cens to tens of thousands, which was closely related to the local lifestyle and conditions (15). Therefore the concentration range of teach mleroplasties was chosen from 0.05 to 1 gL * in this research This concentration did not necessarily represent the concentration of imjeroplastis in real sewage and effluent, but itd a directional effect. Fig. 5 illustrated the impact of microplastic concentration on removal efficiency during eleetrocoagulation. As shown in Fig. 5, generally the removal rate of microplastics was decreasing with the invease of the concentration of mieroplastcs. When the concentration of mieroplastics was selected a€ 0.05, 0.1 and 0.02 g 1%, the removal rate was 89.7%, 92.79% and 88.6% for PE, 93.4%, 87.83 and 79.8% for PNIMA, 86.99%, 85.68% and 83.796 for CA, and 89.2%, 87.956 and 86.5% for PP, respectively, after2 electrocoagulation with Al anode, which i similar to that of previous study (17). The final removal rates of each micro plastic at these three concentrations were all more then 979 (Fg. 5), implying that eletrocoagulation process wit Al anode has excellent removal effect for microplasics with lower concentrations. When the concenteaton of microplsties increased to 1g L", the final removal rates decreased to 87.5% for PE, 87.196 for PMMA, 91.8% for CA, and 94.3% for PP, respeetively. For eleetrocoaguation with Fe anode, the highest removal rates of microplasties were 84.3% for PP, 68.89% for PMMA, 95.6% for CA, and 94.5% for PP, respectively, when the can centration of microplasties was 0.05 g L. The results showed that the removal efficiency ofelectrocoagulation with Al anodewas much betterChel Engen seul 4282022) 121163 Remora etme (6) Recvafcinsy(8) Rema cc (8) é Reara ecnes 8) : zg z i i be = . i, ZB], eat 0 1 2 os 4 : © ai 1 2 a 4 . o Fig. 4 Bet of dient applied voltage ineasty on removal of miropasties dung elcetrocoagulation, than that of eleetrocoagulation with Fe anode for microplastic removs Moreover, compared with granular microplastie PE and PMMA, the removal efficiency of ber microplastic CA and PP by electrocoagulation process was more obvious. Even when the concentration of micto: plastis has reached 0.8 g L, whieh does not exist inthe ral sewage, ‘nd the final removal efficiency was sll more than 958 (Fg. 5). These findings indicated that electrocongulation with AI anode has a bright forure in wastewater treatment, especially in the removal of imicroplasis.M. Stent Chel Engen seul 4282022) 121163 g z i i i emea ices) z i 7 aoe i i i Tom |4 imo) fae ig. Eifet of micoplasleconcenution on removal of microplate during electrocaagulation, 3.2. Removal mechanism produced by anode dissolution (Equation (2), nd with the increase of PH in the reaction process, AP" and Fe” would react with OH ‘The mechanism and process of mieroplastic removal by electro- generated by cathode to from different hydroxides. For Al anode, Al?* ‘congilation were well investigated. Firstly, AI and Fe** were produced by electrolysis rapidly exist in the form of hydrated fon Al(H,003* in water an then quickly hydrolyzes to lose H, forming @ seties of mononuclear complexes, such as AI(H0)s0H?*, AL (,0),08"*, 1(,0),0H°*, etc. The retention time of AP™ in water is long, the hydration of AD with OR is sufieent to form AIOH?*, Al (OH), ANOHS and AL (OH, and the degree of polymerization and ‘yield of polyalumninum are Inge, which is conductive tothe subsequent decontamination (Fig. 6), Due fo the increase of hydroxyl aluminum, jou, the remaining lone par electrons wid the unsaturation of hydroxyl ‘coordination ability, the hydroxyl group ean polymerize with another AD® gradually to form a hydroxyl bridge structure, forming cwo hy. ‘roxy bong bridges. As result, the complex of mononuclear aluninsin (Alg(HH20),(OH);"-"") ean be slowly polymerized into a network of hclear polymers with rch hydroxyl groups on the surface, and Analy transformed into amorphous Noceulant ((AI(OH)s]q). The low degree of polymerization flacculant can remove the microplastis by adsorption, ‘hile the high degree of polymerization Moceulaat can capture and ‘sweep microplastic particles by netting because of its large surface area ‘and many surfaces groups (251. Fig. 7 Hlsteated the morphology’ of AL flocs and Fe floes after coagulation with different microplaste particles. Tr can be seen from the figure thet aluminum flocs are distributed in fakes, while ion floes are distributed in granules. The removal ability of aluminum floes is beter thau that of iron flocs, Fig, 7 showed that the ‘aluminum flocculane with high degree of polymerization is formed in the proces of eleetroconguation, and the microplastis in the water are removed by net catching and sweeping. The results of flocculation ‘experiment showed that the reactor was completely coveted by flocs and there were obvious mieroplastes adsorbed on flocs ‘Aluminum flocculant ean polymerize rapidly under weak alkali conditions, but due to the amphoteric charaeterstes of aluminunt hy. droxide,it is easy to dissociate into Al(OH); when pH istoo high. When ther is sulfate in water, SO2 adsorbed on Alg(H,O'(OH)E * can proaiote the connection of more network polymers du to the attraction ‘of hydrogen bond snd charge. For Fe anode, Fe™* mainly exists in the form of hydrated Fe(HO)8" in water. When encountering with OF” in ‘water, i will be hydrolyzed into a series of mononuclear hydrolysates, such a8 Pe(Hi0)s0H7", Fe(HHz0),0H*", ete. Similarly, dhese mono niclear hydrolysates can polymerize into macromolecular polymers and finally form y-FeOOH precipitates due to che unsaturation of hytroxyl groups ‘Anode: MoM” +36 @ cathode: Chel Engen seul 4282022) 121163 10136-3308 M4 3HLO-M(OH), 4310 @ Inaddition, A]OH™*, AICOH)}, AUOH)s and AL (OH formed inthe reaction process are positively charged, which ean adsorb negatively cluarged fon microplasties. The addition of anionie surfactant ean bance the negative charge on the surface of microplasties in suspen sion solution 22), whieh also makes co- precipitate with mieroplastes in the process of forming Al(OH). This is also an important mechani for the removal of mieroplastes In the process of eleetrocongulation. Electrostatic adsorption: AIOHE! + 2Microplasties AION! — 2Micropstios o AI(OHD + Miroplasties" Al(OH) ~Microplasties o Al(OH)! + SMicroplastics Al,(OH){’ — SMicroplastis a In order to ensure the complete and efficient hydration and poly: merization of metal fons and Mocedlation process, the water low of batch o circulating flow is usually used in electrocoagulation. However, the hydrogen evolition reaction of cathode will produce microbubbles, find the addition of surfactant will make the bubble produetion more {intense (27). When the formation rate is very high, the polymerization ‘of metal ions willbe disturbed, the formation of loceuant will be low, and the degree of polymerization and density wil be smal. 3.3. Comparison with other studies lectrocongulation provides a simple wastewater treatment process, which does not eely on the chemicals or microorganisms used in general ‘heanica coagulation and traditional activated sludge proces [28]. The blectrocongulation process has been sccesflly applied to remove pollutants from sewage, The research on the removal of various pot lutants in sewage by electrocoagulation process was shown in Table | Significantly, che available research on the removal of mleroplasties from wastewater by elecrocoagulation process was very lite. Consequently, ngjestionably, the comparison between this sd and related literature was pale. A research done by Perrea, Wojtasik and Cai (171 investigated the removal performance of PE ticroplstic from simulated wastewater by electrocoagulation. The reslts showed that the removal rate of PE microplastic was measured co be > 90% under al Fig. 6. Mechanism of mixopasie removal fiom water by eleewocongulation processChel Engen seul 4282022) 121163 Fig 7. Morpology of Al floc ad Fe es ater coagulation with liferent ncroplatic particles (FE, PMMA, CA and PP) simulated conditions, and the best removal rate could reach 99.24% under neutral condition (pHt ~ 7.5), In ths study, four mieroplasties were selected, and the removal efficiency was 98.6% for PE, 99.1% for PMMA, 99.996 for CA snd 99.9% for PP under the same experimental conditions Ciable 1, ). In addition, the removal effcieney of fiber microplastics was obviously higher than that of granular micro: plastis. This is mainly due tothe typeof pollutants. The mieroplasties ‘experienced rapid charge neutralization, which ean remove 70% ofthe inital mieroplastics. Inthe remaining operation period, flocculation mechanism played a leading role in purifying wastewater and removing residual microplastes in wastewater. Compared with iron, Muoride, dye, and bleaching efvent(Is0le 1), this combined mechanism allows the renuoval of large number of microplastcs. Despite some limitations of this stdy, considering the removal efficiency and operating costs of tmicroplastis, eleetrocoagulation technology is tensferable and reph cable i laboratory and industry. I¢ is also necessary to optimize the working method and operation tie to further minimize the power and tlectrode consumption,Chel Engen seul 4282022) 121163 ‘Table 1 Removal eet of eentpolitants by electrocoaglaton proces Plant eenedemavtial Renovate __cODrenoval___‘TeSremeral__Optimumintl Reece ‘Donec wane rn ro ee ose . Be en a 958% 7 - 60 (33) Pe manutcuning sage Al : os ow 595 (oe) Stent fe oom . e So 05) ‘leaching eae a = wou oe 70 a Pe misopacse a oom 7 : 25 7 Pe mirepasie a sare : : 7a tis suey 4. Discussion, system, The results of this stidy show that the electrocoagulston Hlecuocomgulation technology has been successfully applied in water/wastewater treatment. Charge neutralization and seavengitg Floceslaton ae two main Mocelation mechanists, and pH vale and current density ae also key paraeters Ii wel known that AP~ and Fe show postive charge duting hyéolis, therefore, the eharacter: ines of foes pay an portant ole in the emoval of mieroplases the congulation process (29). This study has revealed the removal eft cieney aud mechanisms of four common microplates by ecto ‘congulation with Aland Fe anode. The curtent ndings showed thatthe removal effect of aluminum anode eeetrcoagulation technology on tujroplasties was very obvious (>98.6H), respectively. The average patil sizes of allo and Fe Noes were menses to be 174.64 24.3 n and 243.8 36.4 pn, respectively (is. 7). Sal lo size me Inge specie surface are, nd the results showed that Al mode ele trocoagulation technology bas a high removal rate of microplstic in the coagulation process. Compared wih iron anode, luni anode was mote suitable for water/mastewater treatment. The pH value of ‘wastewater has a significant effet onthe removal ffeiency of mico plastics by electeocoagulation, but the pH vale of urban domestic Sewage is 62-9 24], which ius in the best pH range for the emoval ‘of meropastis by eleewocongulation 1m ain, intersting, the eument ndings indeted hat eee trocongulation tecnology has better removal effect on fiber ceo plastics in wastewater (299%), Before tat fiber mieropastis were often neglected i the research field of micropasic [30]. The Biber Injroplasties in wastewater mainly come from synthetic fiber in ry vwstevater,dsended cigaee huts and washable wet rise, ete Cigaterte butts are usually made of cellulose acetate plastic, and one filers usually consists of 15,000 strands of fibers, which ean nctease dhe accumulation of miroplastie fibers ithe euviroument in «short, period of tne (51). Recently, a sy done by Brain, Marques Mendes, MeCirron, Healy and Morrison (321 investigated the material compo Sislon of various white fibers obtained from intertidal sediments near sewage teatment plans, as wel as metoplasties in in the sediments from repeated washing of veal domestic waste. The fudings suggested thatthe micropastie bers extracted rom these wastes were snl 0 those extracted from intertidal sediments neae dhe wastewater eae plant, and the wet wipes and sanitary towels Mushed dawn the drain ‘were an undeestiniated source of white micropastic fibers in the ‘vironment. Nowadays, the consumption of disposable masks as ineresed sharply with the global oubresk of COVID-19, whieh aso inereases the chances of discarded masks entering sewage teatent plants. Evidence has shown that the material of disposable masks polypropylene (9). When these plastic fibers enter the water, the plastic fiber strands will gradually separate and release micro plastic fibers. completely aging insk releases bilions of mieropase bers into theenvironment, which sa great challenger he sewage treatment technology seems to be able to complete the removal of fiber micro plastis in wastewater. Furthermore, the coexistence of different types of mieroplastics and ‘other potent i the sewage will complicate the removal effcieney in the wastewater treatment process, The relationship between the oper acon cost and the removal efficiency of pollutants by electrocoagulation technology should be considered. In addition tothe advantages of in-situ ro secondary pollution, high content of ative ingredients, less sludge, simple device and easy to realize automatic control, eletrocoaglacon tlso shows the characteristics of wider range of polhitents, higher pollutant removal efficiency and lower energy consumption, Electro. coagulation technology also has some problems that cannot be ignored, which may limit the further development of the technology in micro plastic removal, mnily for the following foe points: (1) High conde tivity requirements, In electrochemical technology, to miintain the electrochemical reaction, that i, the low of eurent, the solution must have high conductivity. Therefore, the conductivity ofthe solution will directly affect the mleroplastc removal efficiency snd operation cost of the whole proces. (2) The anode needs tobe replaced regularly. Due to the eleewrochemical dissolution of the anode, ¢ wil consunie n lot of energy for Long time. If the anode is replaced iregulaey, i will easily lead 0 the destruction of the plate and further cause pollution to the water body. (3) Residual metal ions. The metal ious dissolved in. the process of eleetracaagulation have a spontaneous hydrolysis praces. kn Addition to the eleetrocongulation effect, some metal ions will dissolve in water. For example, the residues of Al" and Fe" will lead to high chroma of water and foxie accumulation of huntan Dod, so the post treatment process is generally needed (0 ensure thet the iron and laminin residues im the effluent meet the standard. (4) Anode passivation: anode passivation isthe maa faetor Limiting the application of electrocoagulation technology. The existence of passive film wil sow down the dissoltion rate of anode, reduce the eurrent efficiency and increase the power consumption. Based on the good removal perfor tance of micraplastcs, the eurrentelectrocoagulation process has good economic benefits and market prospects. However he surface chats teristics of various microplastics, the diversity of wastewater and its Impact on the subsequent testment process need to be further ste. AC present, the research of enhanced electrocoagulaion is sil in the laboratory stage with small scale, and most of the veater is synthetic Wastewater, which is still a long way from engineering application. In the farure, researchers need to pay more attention tothe scale-up of the reactor, the treatment efficiency of the actual wastewater, and the conioniie problems, so as o ensure the early and wider application of the electrocoagulation technology. 5. Conclusion Recently, with the continuous attention tothe behavior and fate ofImieroplastics in the environment, i is urgent to understand their removal characteristics in the everent water/wastenater treatment process. This study systematically explored the removal performance ‘and mechanism of four mroplastcs (PE, PMMA, CA and PP) in ‘wastewater by eleetrocoagulation process. The effects of anode material (Al and Fe), pH value, eletrolyte concentration, applied voltage and njeroplasti concentration on the reaction were studied in an electro coagulation reactor. The findings suggested that electrocoagulation technology is an effective method to remave microplesics from sinn Taved wastewater, Compared with the process with Fe anode, AL anode ‘system has better removal effet om all microplasties (>98.6%6), When, {ve intial pH of che influent vas neutral (pH 7.2), the rewoval effect of inicroplastic reached the highest with he final removal rate of 93.296 for PE, 91.7% for PMMA, 98,296 for CA and 98.46 for P, respectively, The removal efficiency of fiber miroplastics (CA and PD) by electro coagulation is better than that of granular mictoplastcs (PE and PMMA}. The microplastic removal efficiencies inereased with the in- ‘crease of electrolyte concentration and applied voltage density, while he floes produced in the reaction process obviously increased and the electrode was seriously damaged. The consumption of electrolyte and ‘other energy consumption inthe process of electrocoagulation should be considered. in addition, in the process of electrocoagulation, micro plastics undergo Noceulation and charge neutralization a the same ce Flocs can capture and sweep mieroplasties by charge attraction and ‘adsorption and the results of flocculation experiment showed that the reactor was completely covered by floes and there were obvious imjeroplastics adsorbed on flocs. By improving the electrocoagulation reactor, the operation cost of the reactor ean be reduced by using these ‘ovo mechanisms. Ii suggested to further study the effet of reducing lectrolyte concentration and current density of electracoagulation, ‘operation efficiency and cost, Further research should focus on the possible reactor design and improvement to optimize the process and realize the repliation and transfer from the laboratory to the sewage treatment plant. Declaration of Competing Interest The authors declare that they have no known competing financial Interests or personal relationships that could have appeared to influence the work reported in this pape, Acknowledgements ‘The study is financially supported by the National Natural Science Foundation of China (82003363, 82073449, 20420923, 51521006) ‘and the Natural Science Foundation of Changsha (k2007059). Appendix A. Supplementary data ‘Supplementary data to this article can be found online at his /do (0rg/10.1016/5.c¢,.2021.191161. References (1 a Sten a, W- Maan. 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