Application of pine bark as a sorbent for organic pollutants in effluents Isabel Bras LEPAE ~ Laboratério de Engenharia de Processos, Ambiente ¢ Energia, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Roberto Frias, Porto, Portugal Departamento de Engenharia do Ambiente, Escola Superior de Tecnologia de Viseu, Instituto Politéenico de Viseu, Portugal Luis Teixeira Lemos Departamento de Engenharia do Ambiente, Escola Superior de Tecnologia de Viseu, Instituto Politéenico de Viseu, Portugal Arminda Alves LEPAE ~ Laboratorio de Engenharia de Processos, Ambiente e Energia, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Roberto Frias, Porto, Portugal M. Fernando R. Pereira LCM — Laboratévio de Catdlise e Materiais, DEQ, Faculdade de Engenharia da Universidade do Porto, Portugal Keywords Water treatment, Trade effuents, Portugel, Natural resources, Wood. Abstract Nowadays trace organic poDutants represent a major concern in waler treatment spstems. Acteaied carbon has ben used for most applications aiming atthe reduction ofthese ‘ind of compounds in aqueous aflents, but regeneration needs and Rgh operation cass led to a ‘renewed interest the search for alternative sorbents. Pina bark san ecadentery ro material {from soxomils in Portugal and therefore a profitable natural resource that has already Been ‘succesful tested inthe adsonpton of rganochlorinas from contaminated water. Ths study is at characterizing the pina bak surface structural and chemical, to aiderstand the natere of Ssonttion occurring when a trace organic contaminant is present in opueous fuente. Pentechorephenol (PCP) was the ince contaminant used inthe experiments. Scanning electron microscopy (SEND, mercury poresimatry, Fourier transform infrared spectroscopy (FTIR) and Xray photodlectron specivoscofy (XPS) were the tecaiques used, in adton to classical chemical ‘sna and sokd phase micro extraction (SPMB) prior to gas chromatography with mass spectrometry (GCMS for PCP quantification. The pine bark proved to be a materia of very low ‘The carent imu and fll eat archive ofthis journal ie aval at worwameraldneight com/477-7836.him Application of pine bark as a sorbent 491 her 24h was ahve 98 per cnt Tis materi provd tobe an encouraging rbot for chagp © awsome Piet ‘water remediation solutions.once in the environment as protonated or anionic species according to the surrounding pH, with a pK, of 4.75. In its neutral form it is strongly hydrophobic (og Koy 524) with low aqueous solubility (l4mg/l at 20°C) and behave like the hydrophobic non-ionisable organic compounds (HOC) partitioning between the organic matter of the soil and organoclays by hydrophobic bonding (Boyd et al, 1988; DiVincenzo and Sparks, 1997), ‘The main objective ofthis study is to evaluate the physical and chemical properties of pine bark and its interactions with PCP, assessing the extent of PCP binding in the pine bark surface through sorption and desorption equilibrium studies, Materials and methods Pine bark preparation and characterization techniques ‘The pine bark was collected in a sawmill in the north of Portugal. After grinding in 2 Reischt mill and sieved in Endecotts EFL 2000/1 automatic siever, the 150-450 yam size of bark was dried at 105C+2°C for 48h in a Binder muffle. The textural characterization was performed by mercury porosimetry with a Poremaster-60 (Quantachrome apparatus, The pine bark characterization was also done by proximate analysis with a Mettler TA 4000 thermal analyzer and by elemental analysis with a CARLO ERBA 1108 Elemental Analyser. The determination of surface charge was performed by pH drift tests described elsewhere (Rivera Utrilla ef al, 2001) and the basicity and acidity surface determination was earlier reported eloewhere Pereira eta, 2008), ‘The pine bark DRIFT spectra was carried out in a Nicolet S10P FT-IR spectrometer. The spectra were recorded at 4em”* resolution and 256 scans were accumulated prior to Fourier transformation and expressed in transmitance in the 4,000-450cm™? range. ‘The elements at the surface were analysed by Xray photoelectron spectroscopy (XPS) with a VG Scientific ESCALAB 200A spectrometer and the scanning electron microscopy (GEM) was performed by JEOL JSM-6301F microscope after sample preparation by pulverization and vaporization of carbon and gold in a JEOL JFC 100 apparatus at CEMUP (Centro de Materiais da Universidade do Porto). Reagents Pentachlorophenol (PCP) was obtained from Supelco (Cat n-4-8555). Sodium sulfate anhydrous pa. and 95.97 per cent sulfuric acid p.a. were purchased from Merck. The aqueous PCP solutions of various concentrations were prepared from an intermediate Simg/l PCP solution made from a 2,440 mg stock solution in 0.1M NaOH (Merck) with distilled and deionised water. The standards preparation for solid-phase ‘microextraction calibration was done by dilution af the intermediate stock solution with distilled and deionised water at pH value 2 saturated with Na,So,, The pH adjustment was done with SN sulphuric acid. Sorption studies ‘The equilibrium sorption and desorption experiments of PCP on pine barle were conducted in 15ml closed glass tubes in a shalker at 25°C, The required equilibrium time of 24h was previously determined in kinetic studies with solutions of 1 mg/l PCP ina system with solid:solution ratio af 1:100 (w:w). In each tube, 100mg of pine bark and 5ml of PCP solutions with concentrations between 0.03 and Smg/l at pH value 2 Application of pine bark as a sorbent 493MEQ were added. After reaching equilibrium, the pine bari was allowed to settle at the | 155 bottom of the tubes and the maximum amount of solution was removed from each reaction vessel for PCP analysis and replaced by Sml af PCP free eolution, The glass I tubes were placed again in the shaker at 25°C. After 24h the solutions were once again removed for analysis of PCP by solid-phase microextraction (PME). 494 PCP analysis —————— For PCP quantification, an 85am pa fiber (Supelco, Cat. No. PN 57304) and the respective SPME sampling manual holder (Supelco, Cat. No. 57330-U) were employed. ‘The fiber was previously conditioned at 300°C for 2h in the gas chromatograph injection port, For the extraction of PCP, 2m! of the standard solution or sample were ‘measured into a 4 ml amber vial and the fiber was immersed in the solution for 30min, ‘at oom temperature (25 2°C), with rapid and constant stirring. After this period, the ‘fiber was removed and desorbed in the GC injection port for 3min, ‘The quantification of PCP was attained with an Agilent 6890 Series gas Shromatograph (GC) equipped with a 5973 N Series mass spectrophotometer (MS) ‘selective detector in SIM mode acquiring fragments with 264, 266 and 268 atomic mass unit (amu). The interface temperature was 160°C and the ion source (electron ionization) was set at 230°C with electron energy of 69.9eV, whilst the quadrupole ‘mass filter was kept at 150°C. The capillary column was a Hewlett-Packard SMS (G0m x 0.25 mm x 0.25,.m) (cat. HP 19091S-433). Helium (89,9990 per cent purity) was the carrier gas, ata 1 ml/min constant flow through the column, The oven was intially ‘set at 80°C, and then raised to 250°C at 15°C/min. The injector was in splitiess mode at 250°C, closed for Simin before purging with helium at 20 ml/min. The calibration curve af SPME for PCP quantification was performed with six standard solutions within a conoentration range of 08 yg/l to 40 yg/l with good linearity (7? = 0.9953). The detection limit calculated, by 3* S/N ratio, was 1.99 yg/1 with a repeatability of 23.82 per cent (as coefficient of variation, CV per cent) and an intermediate precision of 15.70 per cent (as coefficient af variation, CV per cent), Results and discussion ‘ine bark characterization Fine bark is usually characterised in terms of its main constituents like cellulose, lignin or tannins, in order to take advantage of their potentials. Nevertheless, to evaluate its sorbent capacity it is important to know the surface properties and their ability to interact with the surrounding medium, Hence, the first step ofthe present work was to Perform the characterization of the pine bark in order to realize the possible Mechanistic interactions between the PCP and the surface. The physical properties obtained by mercury porosimetry are shown in Table I The data are consistent with i ‘SEM images shown in Figure 1. in fact, the pine bark eurface has low porosity and the ~ Values Real desi (gem) 134 Table 1 Pore volume e/g) aio Physical properticn af a7few pores detected are classified as macropores (according to TUPAC with diameter higher than 50m) leading to a very low specific surface area. “The proximate and elemental analyses allow us to know the overall composition of the bark while the XPS and FTIR information take into account the surface chemistry. ‘The volatiles, fixed carbon and ash content obtained by proximate analysis were 73.16 per cent, 2647 per cent and 0.37 per cent (w:w in dry basis), respectively. The organic ‘matter content of this material can be found by the sum of volatiles and fixed carbon, attaining a value of 99.63 per cent (w:w in dry basis). By elemental analysis it was possible to verify that the organic matter was made up of 55.80 per oent af C, 597 er cent of H, 3759 per cent of O and 0.64 per cent of N (wm). ‘With the XPS, 82.18 per cent of C, 1721 per cent of O and 0.63 per cent of N were ‘identified at the surface of pine bark (atomic percentage, with spectrum peak areas divided by the corresponding sensitivity factors — C: 1.00, O: 298 and N: 1.80) taking into acoount that the low mass of hydrogen is not detected by the technique. The chemical bond analysis was made by curve fitting using the XPSPEAK 4.1 software, deconvoluting the Ci, peak in four subpeaks Figure 2) with binding energy corresponding to different functional classes: Cy corresponds to the aliphatic and aromatic C—C and CH bonding (285 eV); Cz to non carbony] oxygen bond, C—OH and C~O-C (2864 eV}; Cy to carbony! oxygen bond, C=O (@287.8eV); and Cy to carboxy] oxygen, COOH and COO— (289.2eV) (Shchukarev et al, 2002; Sinn et al, 2001), The highest percentage was attained for carbon-carbon bonding, with 73 per cent, siving an idea about the strong magnitude of aromatic bonds assigned tothe pine bark: lignin and extractable fraction. The hydroxyl bonds represent 18 per cent of the carbon associated to the hollocellulose and phenolic content of the baric. The less representative bonding classes were the C, with 64 per cent and the C, with 23 ‘pet cent, probably related with the extractable content of the bark. Another technique applied to complete the pine bark characterization was the FTIR, although the surface complexity and heterogencity were unable to readily characterize the absorbed infrared light at specific frequencies. In fat, the information acquired is ony qualitative inthe study of specific structures a the surface, The spectrum can be divided into four regions, namely the region between 4,000-2,500cm for stretching vibrations of X—H bonds, 2,500-2,000cm™* for the triple bonds, 2,000-1,500 em™? for Application of pine bark as 2 sorbent 495 Figure 1. SEM images of eieved pine barca) amplified 10,00 times; () amplified $5000 timesbonding. The band at 2900 m=" ¥s assigned trick © aliphatic structures and the absorption ide Wdentified due to the aromatic OmC skeletal vibrations and a weak band around 1,735cm"* caused by the stretching vibrations { C=O carbony! structure, Gouble bonds and the imown finger print region between 1,500-650 cm". As can be i rae aren 340Dem the mpc represents hoes and ee A 280 ee eroeeN stretching vibration, including 2 Weave number (om)One important broad band is identified around 1,160cm~+ as a result of the sapete stretching of C-O-C in the clilose and hemiceliuoee (Vésquez eta, With the FTIR analysis it was possible to certify the XPS results identifying the ‘weight af the C=C aromatic bonding, the phenolic and polysaccarides hydroxyl group along with the C—O—C bonds and the double bonds between the carbon and oxygen atoms in the carbonyl and carboxy! groups. These kinds of structures are important in the perception of possible interactions with the surrounding molecules and the hhydroxylic can be classified as acids once they can loose the associated hydrogen proton; on the other hand, the carbonyl group with the strong electronegative oxygen ‘tom can accept hydrogen atoms behaving as a base. The pine bark acidity and basicity determination showed once again the importance of the surface acidic groups With values of 5.58meq HCL for the acidity and 0.08 meq NaOH/g for the basiity, ‘The attempt o evaluate the pH ofthe point of zero charge ~ pH at which the surface ‘has an equal number of negative and positive charges showed that the pine bark always has an acidic behaviour with an equilibrium pH around 4.4 (Figure 4). ‘Tae presence of oxygen and hydrogen atoms on the pine bark surface along with its ‘aromatic structure may induce that the solute molecules can establish hydrogen bonds and hydrophobic interactions with the sorbent. Sorption Although other models are mentioned in literature, the most applied to describe ‘Sorption in wastewater systems are the linear (equation 1), the Freundlich (equation 2) and the Langmuir (equation 3). = Kit, a = Kpecl @ QPabec, 1+d*C, ® In these equations, ¢, and C, are the solute concentration in the solid and in the aqueous hase, respectively. For each equation, K, is defined as the distribution coefficient in % Application of pine bark as a sorbent. 497the linear isotherm, Kr and Um are related to the sarpt ty and the * PES ent te cp ae ee Lindane ‘ine bark conducct 7 ‘resented the Freundlich isotherm as the best madel fo describe the collie nt = 2 . | 2.080) oe Si and 3 1 dat fr pine 2.000 —_ ° ~ - sbtained for Kye) 7? isotherms by ST ———~ Seemion 15006 ase om sO Liason ome 9245 o2=10 ame PO SFSREHPRRARER GRasneeenoe we mewith Kp of 0928Vg and Un of 1,01 for Lindane and 70.78Vg and Wn of 121 for Heptachlor. ‘The good sorption capacity of the pine bark once verified, it was intended to study the reversibility of the phenomena. A preliminary evaluation of desorption from the pine bark surface was performed using a batch washing (Figure 5). The Ky attained in the desorption, 6.14V/g (r? = 0.937), was higher than the sorption K. The deviation ofthe desorption equilibrium data relatively tothe eorption data is representative of sorption irreversibility, providing evidence that the PCP establishes a strong bonding with the solid phase. Karichkotf et al (1979) stated that the linear isotherm is often indicative of partitioning. Indeed, if a PCP partitioning existe between the organic solid phase and the aqueous phase, induced by the strong affinity of the organic pollutant to the organic phase, itis expected that the reverse situation would not occur. Chen etal (2004) studied the sorption and desorption of PCP in soils and also acoomplished that the sorption had a linear behaviour and found strong evidences of hysteresis. They suggest that the chemical composition and the condensed rigid physical character of lipids enable them to interact more strongly with the hydrophobic organic solutes via weak van der Waals bonds, General reasons accepted to cause sorption hysteresis are related to experimental artefacts, irreversible binding to specific sorption sites, slow rates of desorption and sorbing molecule entrapment (Chen et al, 2004), To override the effects of experimental artefacts a blank experiment was conducted without pine bark but following the same experimental procedures and the sorption and desorption experiment was conducted ‘under the same conditions, Owing to the pine bark low porosity itis unlikely that the entrapment of the PCP molecales was the cause of the observed hysteresis Accordingly, itis reliable to conclude that the sorption irreversibility is assigned to the irreversible binding to specific sites of the pine bark or slow rates of desorption. In effect, hydrophobic compounds with such high log Ka, as PCP will have strong affinities to organic matter matrices with representative aromatic content as pine bark. ‘Whichever the case, it can be stated that the PCP in the pine bark can be considered to be stabilized, reducing effectively the mobility of this hazard pollutant in the environment. Conclusion From the results of the present work, it can be concluded that: (Q) Pine bark is a material with small porosity, with the few pores identified in the range of macropores, and therefore with emall specific surface area; (2 The bark has very low content in ashes with the organic matter representing ‘more than 99 per cent of the weight. XPS and FTIR characterization of the surface chemistry show the expected presence of C—C aliphatic and aromatic bonds and C—O bonds from the hydroxy!, phenolic carbonyl and carboxyl groups, the last two assigned to the extractable fraction of the bark; @) The sorption of PCP can be described by a linear isotherm, suggesting that the ‘sorption is due to the PCP partitioning between the aqueous and the solid phase; and (4) The conducted desorption experiment show that the PCP is strongly bonded to the pine bark surface. Application of pine bark as a sorbent 499MEQ Tbemain conciusion ofthe present work i that the pine bark can act as an effective 155 fofbent for POP being 2 good altemative to conventional sorbents, which ape, ” {Gilly immoblies this organic pollutant with all the benefite associates vik Qeosst of local and abundant residues. Alves, MM. Besa, CGG, Guedes de Carvalho, R, Castcheira, JM, Peri, MCS, and Finer eas, LAT (1989, “Chromium enol in tannery wastewaters posing te Pinus sists bark’, Water Research, Vol 27 No.8 pp. 13838. Bord, Ss Shasba, S» Les IF. and Mordand, MM, (989, “Patachorophenol sorption by organo-lays", Clays and Clay Minerals, Vol. 35 No. 2, pp. 12530 ris IP, Santos, Land Alves, A. (1900), “Organochlrine pesticides removal by pins» bar sorption’, Ennironmental Science Technology, Val. $3 No. & pp. 681. Gren, ¥ Chan H, Xa, Y. and Sten, M. 2008, “reverie sorption of pentachlorophenal o ecient: experimental observations", Enivonment Iterationdl, VOL 3)Na Ter ck Crosby, D. (9a, sr ggumental chemistry cf pentacloropheno!”, Pare and Applied Chemisty, ‘Vol 83, pp. 1051-80, Pivincens, JP. end Sparks, DI. (967, “Slow sorption of pentachcropheso! on soit cenosization effec, Savonmentl Scone & Tochoobay, Val Bt oe ek Fenge), D, and Wegener, G. (1968), Wood — Chemistry, Ulrasiractre, Reactions, De Gruyter, Frade DM, Neo, CP, Evtuguin,D, Jog F.C, Ie M.A, Gi, MH, and Jens JP. 2002, {Cherie carnation of back and aialine bark ext om tae po ok in Portugal’, induct! Oops and Pordacts, Val 1BNO one ee aru nd Labo.) 1965), “Chemical conan five northeast bara, Wood and Fiber Scone, Vol 17 No.2 pp. 48 Hunard M, Gabalah 1, Kane N, de Donat, Py Bars D, sed Vigan, F 209, Tapani of hrdocarbons Sd ii rom wate unog teat bask ase ee Vol 37'No. pp. 36274, ¥omoa, WY Peng. P. YZ and PJ 200) "tts fergie mater helen ca sorption ‘nd of gmc cxtaminans by eos and sedinetsAppied Comores Vol 18.7 pp. 5872 4ocas EC, Bro, P Pepin L, Portugal A, GH. and Osta RP), Aoliagtes par ae Sarge de Arvorse pare on Extracts Tanzesos: Un Revises Abe Lote vas 0.2, op, 22598, Xerickin, SW, Brown DS. end Scot, 7. (1979), “Sorption of hydrophobic polltans on natural sediments", Water Restarch, Vol 93 Ne oe oak Pereira, MPR, Soares, SP, Orfio, JJM. and Figueiredo, JL, “Adsorption of dyes on aclvated carbons infuence of euace chemical grompes Carne Tene 4 Si nT ve veze st se ° n ” Randel JM G07? Variation in efecsivenes of barks on wcavengers for heavy metal ond", Application of ‘Forest Products Journal Vol 27 Nos pp SL i Rate, N, Boteho, Cand Alves, A. @009, “The uoe of pie bark asa natural adsorbent for PIN bark as a Pest organic pollutants study of lindane and heplachior adoption oseed sorbent Ghemical Technology end Biotechnology, Vol. 78 Nos 25 pp. 347.6 MA, and Moreno-Castila, C. 200), “Activated Gaibon modifications by adsorption af bacteria and ther eflect On shun wed 501 | Chem. Technology ad Boteckrolgy, Vol 76 No. 12 pp. 1208 16 ——_— Nand Carvalho, JR. 2009), “Biowrption of copper by Procisang and Sehularey, A. Sundberg, B, Mellrowics FE. and Person, . (200, “XPS study of ving tre" ‘Surface and Interface Anaiyes, Vol 34 No. 1, pp. 2848. Sinn, G. Reterer, A. and Suna! Techegs, E, 2001), “Saface anys of diferent wood species Pe ese Photorlectron spectroscopy (XPS), Joumalof Materials Science, Vol 36.15, 1p. 4673-80, Tanjore, Sand Vireraghavan, T. (997), “Btfect of oxygen on the adsorption of Rewaclorenhenol by peat from water, Water, Air and Sol Palution 1997, Vor 160 Nos 12, pp. 151-42. ‘Viaues G. Freire S- Gonzey, J and Antorren, 200), "Characterization of Pinus Pinaster ber and ts liane extracts by diffuse reflectance Fourier transara sfarel ORI) spectroscopy”, Hole als Rob- und Werkstof, Vol 68 No. 1, yp. 57-6 Visors, G- CouslerAtvares, 1, Fret 8, LéperLoreaza, M. and Antrrena, G. Q002, Removal of cadmium and merry ions from aqueous soktion by sorption ox etc Pines Pinaser bark: Yinetis and isotherms’, Bloresource Technology, Vol. 2 No pp. 2761.