Surface Complexation Modeling™ $ Golders, USDA-ARS US. Sanity Laboratory, Rivers, CA USA © 2018 Bowie. lights reseed Invoduction 1 Description of Models 2 ‘SuraceConguaion ofthe Sold- Soliton neice 2 ‘Surface Complexation Reactions 2 Eaulvim Constant or Surface Complexation 4 Mass and Charge Balances 5 Ciarge-Pototal Relationships 6 Otainng Values of Adjustable Parameters 6 Surface Ste Densty 6 Capacances 6 Surface Complexation Constants 6 ‘Applications to lon Adsorption on Natural Samples 1 Constant Caaciance Model 7 Diese Layer Madel 8 “Tile-Layer Medel 1 One-pk Model a Symbols Ny Maximum sue ste density [ates nm" (@gh Sanda deion ref beh daaset RM gos") Pantie concentration [g1™] SS Surfacearea [rg] A Aolon of the background decwoine SOH Reactive srice hydroxyls bound toa mel ion § © Capacitance [Fm S, Highafiniy ses Cr Gatlon ofthe badground eecnolte St Total mmber of reactive surface functional ©, Gapacancebevern the o- and dhe Pplane ous [em] Se Lowa ses Cy Capacitance between he feandthedplane Tbe temperate [X] lee] ] - aye ] = [80 -c"] ta, p= m{SO- ~ MP] + (m ~1) 80" — MOH] +.[80" ~ c*] - 1[soH} —L'"] - (1 - [sony — LH] — [Song - a7) [42] asa} nt=0 (4s) Foleronce Module in Earth Systems and Environmental Sciences, (2018)5 Surface Complexation Modeling ‘where © is the surfce charge. The charge balances, [21] and [42], represent the summation of all charge contributions in a paicular plane of adsorption. All of the models consider charge balance in the surface plane, eqn [41]. Charge balance in the Plane, eqn [42], is restricted to the wiplelayer model. Charge balance eqn [13a] is considered in the wiple layer mode while eqn [435] is used inthe difuse-layer model. The charge balance expressions forthe one-pK model based on the Stem ‘model are eqn [436] and: ([souy*] - [sor] fas} Charge-Potetial Relations {All surface compleration models contain relations between surface charges and surface potentials, Inthe constant capacitance ‘model the charge-potential relationship is a= ks} here Cis the capacitance. The charge potential relationship forthe difuse layer model is 64 = ~(8e:DRTD"” sinh (F¥4/2RT) las} ‘where isthe permittivity of vacuum, D isthe dielectric constant of water, and isthe eolution ionic stength. In the wiplelayer ‘model the charge potential relationships are eqn [46] and: 4% = Ci(Po~ 4) («7 4 =Ca(Pa— ¥) 3] “The charge potential relationships for the one-pK model based on the Stezn model ar eqn [46] and = Clo ~ a) {4} Obtaining Values of Adjustable Parameters Surface Site Density ‘Thetotal number of reactive surface functional groups, Sys an important adjustable parameter in the surface complexation models and is related to the surface site density: sO Ns {50} where is the surface are, ai the particle concentration, and Nis Avogadro's umber Experimental methods for determining surface ste density inchide: tritium exchange, potentiometic tation, Suoride adsorption, and maximum adsorption, Values of this parameter can also be calculate from cystal dimensions or optimized to ft experimental adsorption data. Various determi- nations of surface site density vary by an order of magnitude; the lowest values are obtained from crystallographic ealulations while tim exchange yields the highest values. Uncertainty in the value ofthe surface site density ia major limitation inthe use of surface complexation models since the abiliy of the models to describe adsorption is sesitvely dependent on this value. ‘To standardize surface complexation modeling, a fied value of 2.31 sites am™* has been used for many natural mates ‘Applications of the difise layer model to metal adsomption have split the total numberof reactive surface functional groups imo a'strong’S, and aweak,’ Sy stof adsorption sts, Thisapproach greatly increases the number of adjustable parameters since ‘each set of sites, 5, has its own protonation, dissociation, and metal surface complezation constants capacitances Some values of capacitance (C in the constant capacitance and one-pK model and Cy inthe wiple layer model) can be obtained ‘gaphially from slopes of protonation- > as 6 7 6 9 pH Figure Fito the constant capatnce mace o sila adsorion on gosh. Mode resus are represented by sold nes. © 2 10~4M; 11410 M4 B10-*M. Rapitd from Sig, LM. ané Stumm, W. (1981). The nracton of anions an wen acids with te hycrousgoetite (@-FeOOH) suc. In: Cots and Surtces, vl. 2, pp. 101-117. Amsterdam: EsvierSeece. content. These surface completion constants were then used in the constant capacitance model to predict borate adsorption on the new soils. This approach constitutes a completely independent model evaluation that was able to predict borate adsorption ona diverse set of soils having a wide range of chemical properties, 2s indicated in Figure 5. ‘Tis soll approach was also used successfully to predict molybdate adsorption fom the chemical properties: cation exchange capacity, organic and inorganic carbon content, and iron oxide content a8 well at asenate and selenite adsorption using fie soil ‘hemical properties. Dittuse-Layer Model ‘The diffuselayer model has been used to describe adsorption on iron, aluminum, manganest,tianium, and silicon oxides, Jaolinite, montmorillonite and biotite minerals, natural organic matter, bacterial cell walls, and sediments. Adsorbing ion that have been investigated include the cation and metal ions: caleium, strontium, barium, copper, nickel, nc cadmium, lad, cobalt, aluminum, chromium, ser, mercury, uranium and the anions: phosphate, sulfate, selenite, selenate arsenate, arsenite, borate, go 1 2 £100 3 fe stators Pehl so % whe | 40] r 20 oe °% 6 8 104 6 8 10 ° oA oH Figure 4_ (a) Fit ofthe constant apactance mode to eset adsorpion ona Calfoia sl. Model tis eresented by so ne.) Constant absclance mode prediction of slate adsorption by Caf sos. Macel predictions are epresetd by so nes. Reprints vith permission rom Spost, de Wit JCM, and Nel RL, (188). Slee adserpton on all sts Il Chemial motsng Sol Senor Sony of Americ ouma $2, 47-850. third chromate surface comple, [SCrO,*-], With this addition, the mode! is well abe to descibe chromate adsorption at all chromate concentrations over a wide ringe of solution pH. "Adsorption of various metal ions has been investigated on a ignocehulose organic substrate exacted from wheat bran. In these applications, wo sets of reactive surface functional groups are considered representing earboxylc and phenolic sie. Figure 8 presents the ability of the difuse-layer model wo describe copper adsorption edges on this organic material asa function of init copper concentration [Cup solution pH, and ionic strength, I In this application, the model i ted to the data for [Ca 210" M, =0.1. The model parameters resulting fom this optimization were then used to predict the remaining model results ‘depicted in Figure 8, The diffuse layer mode is well able o describe copper adsorption on this natural material "The diffuse layer model has ben used to describe arsenic adsorption by a contaminated sol profile. In this application it was assumed that amorphous iron oxide was the principal reacive adsoibent. The modeling was sucessful in describing arsenic adsorption in the two ayes containing the most extractable ron. Feference Madule in Earth Systoms and Environmental Scences, 2018)10__ Surface Complexation Modeling rn a LT on mm ‘gure 5 _Corstncapatarce mode! pesiction of born adsorption by sols of vara sl cemical properties and ers ol ord. Model ‘edicionsare represented by sold ines. Modif from Golberg, , Leech, SM, and Suarez, DL. (200), Preto boron adsorption by sols using ‘alchemical parameters inthe constant eapctance model, Sol Siace of Solty of America uma 4, 1356-136 18 sorbed (uot) ‘gure 6. Fit of te atuse layer modelo lead adsrptononhemabi. Malis are represen by sli ws. 100 yo": 20 uma, ‘244 ynol I Reprocuce wth permission fom Cis and Kretzschmar, (1899). Compal sorption of oppe nd ead at he oide-vater Inertace:impieatons for sufce se deny. Geochimica et Cosmochim Acts 6, 2828-288, 100: ame nee Clase? ora emma Sue One| eH FRgure 7 itt tease layer modelo chromate adsorpton on goeite. Model fs ae represented ty sl Ines. © 0.01 mol (©005mmol- O2rml © 08 mmol Reprint with emission or Mesure, K and Fh, W. (862). Cvorae and xa adsorption ‘on poet: Cairaion of surface camplxaton mel. Enironmantal Science and Tecnology 28, 2357-2264. Cpyight Amwcan Chemical Soe Fference Module in Earth Systoms and Envicnmental Sciances, 2018)‘Surface Complexation Modeling 11 100 sa oH Figure Ff the ise layer modelo copper adsorton on gnoceose exacted rom whet ban, Mods ts ar represented by sod es. ‘2 CU(INje=210-* ma 1=0.1; @ [CulNam2.10°* mal = 0.0; + [C(Iju=2.10-* mel, =O. Reproduced with parison ‘fom Rav, C,Duronceau, i, and Monte, 200} Acs and Cl ning properties of rata organ mate exacted om wheat ‘ban: modeling bythe surface completion node Water Research 34, 1827-1228, 10 08| 08 oa Fractional adsorption of Pb 02] ‘Figure 8 Fo te trle-Syermosel to adsorption on gost. Mose is ar representa by sold nes. 0 9.85 ymol I @ 24.1 mal: 1748.3 uma, ¥ 724 unl I~. Raproduced wth pemision tom Kooe, ZS. Cox C.D. and Smoot, JL (186). rein of sisorpon of valent hay metals at the gotievaterittae by surface completion medelng. Evironment Toxtcloy and Chemis 14, 2077-2088. Copyght SETAC, Pensacola, Fld, USA ‘Trple-Layer Model ‘The wiple-layer model has been used to describe adsorption on ion, aluminum, manganese, and silicon oxides, kaolinite and smectite clay minerals, and sols Asorbing ions that ave ben investigated include he cation and meual ions: sodium, potassium, calcium, magnesium, lee, zing, cadmium, copper, cobalt, silver, mercury, uranium, plutonium, thorium, neptunium, and the anions chloride, nate, perchlorate, sulfate, selenite, selenate, arsenate, arsenite, molybdate, borate, chromate silicate, Hride, carbonate, alate, phthalate, salicylate, lactate, acetate, formate, and humate “The ability of the tiple layer model to describe metal fon adsorption edges is depicted in Figure 9 for lead adsorption on gocthite. In this application an innerspere surface complex is assumed. The wiplelayer model was well able to descibe lead Reference Module n Earth Systems end Environmental Scinss, (2018)Figure 10_ Fito the tipeayer mode tselenate adsorption on arphous ron vite. Mode! sare reprserte by sod nes Total $20, ded © 240°" moll" = 2 10°® moll“; a 2x 10-*mall"s©2>10-*mal |. Repeduoe with permission rom Davis A and Leck, 4.0. (180) Sure onan and competion the oxide itrtoe. Il, Aésomtion of anor. Journal of Cold Itare Scene 74,8213. 100] & & O10, adsorbed g gure 11 itf the trpleayer mode to chromate adsorption onto sls. Made sae represene by sod nes. c Host Goud series sal CecvPacolt ser so, Reprints with permission rom Zactara, JM, Answort, CC, Cowen CE, and Resch CT. (1985). Adsorption of chromate by subsurface sl horizons. Sl Since o America ours $9, 418-428. sdsorption at various intl concentrations asa function of olution pH. Figure 10 shows theft ofthe wiple layer model o anion adsorption envelopes for selenate adsorption on the iron oxide, fersiydite, With the assumption of two outer-sphere surface Completes, the model describes the adsorption data quantitatively forfour vasly diferin intial selenium concentations 35 2 function of toluion pH. “The tiple-layer model was able to ft alum, magnesium, and sulfate adsorption ona Brazilian oxisol and sulfate adsorption ‘on an acidic forest soll. Molybdate adsorption on two Califomian soils as @ function of solution pF and ionic strength could be described using either an innersphere or an outersphere adsorption mechanism. The quality ofthe it was slighty beter with the innersphere adsorption mechanism. In this application i was assumed that aluminel groups on the dy edges are the reactive surface funcional groups in the soils and that surface complexation constants determined for reactive surface hydroxyls of sluminum oxide can be used to describe the surface compleration reactions undergone by these aluminol groups. Tia similar approach, surface complexation constants previously determined for the reactions undergone by aluminum- substituted goethite were used to describe chromate adsorption by two soils. It was assumed that only the Ion sites on the shuminum-substtated gpetite ae involved in chromate adsorption, forming monodentate outersphere surface complexes. The ability ofthe model to describe chromate adsorption onthe wo sols as function of solution pH isindicated in Figure 11. Theft ofthe model on these heterogeneous materials is qualitatively correc. “The general regression model prediction equation approach was incorporated into the triple layer model and used to describe ‘molybdate adsorption by soils Using borhan innersphere and an outer-sphere surface configuration the model prediction of ‘molybdenum adsorption was improved over that obtained using the constant capaciance model, especialy at high solution pE FRoference Module in Earth Systm and Environmental Sciences, (2013)Surface Complexation Modeling 13 One-pk Mode! ‘The one-pK model has been used to describe adsorption on iron, akuminum, and titanium oxides. The vast majority of sues to date have used goetite atthe adsorbent material, Adsorbing ions that have been investigated Include the cations: potassium, calcium, cadmium, copper, and anions: phosphate, arsenate, selenite, sulfate, chromate, lactate omalate, malonate, phthalate, date, and falate, “The abiliy of the Stern model based one-pK model to fit cation adsorption isotherms i indicated in Figure 12 for cadmium adsorption on hematite. The model was well able ta describe cadmium adsorption at various solution pH values and initial ‘cadmium concentrations. In ths aplication, consideration of background elecrolyte surface complexes was neglected. Figure 13, indicates the abiliy of the Stem model based one-pK model to fit anion adsorption isotherms for phosphate adsorption on ‘octhit The model wat well able to describe phosphate adsorption over a very wide range of solution pH values and initial ‘Phosphate concentrations. In thi aplication, a surface complexation constant for potassium adsorption was also optimized + tog (oo ‘awe 12 Foleo 9K modelo cadmium adsorp on amerphots ron ox od ae eps ysl ees. © 7.2; ‘474; 77; +80, Reprod wih persion rom van First WA, de Wi, CM, Koopal LK and Bo, ., (197). Metal adsorption on Feterogenous surfaces adsorption modes. Jounal o alo Intetce Scene 16, $1152 25 o cy " a) oa Oz 0a 36 ‘Solution P (mmol) Figure 18_ Fit of the one-pK malo phosghate adsorption on gost, Macs are represen by Sli lie. Reproducid wih permission ‘rom van Ried, WLM. and van do 28 AM, (191), Comparisons of Mocels or Adsorption, Sold Sluion nd Surface Precipitation oases on eiperimatal daa of Bowden etl (786). Bo, GH. al. (ds) ntractonsa he Sl Cold-Sl Soutien inetace, pp. 241-286, orcect, ‘he Netertands Ker. Reference Module In Earth Systems and Enviranmental Sciances, (2018)14 Surface Complexation Modeling “The CD-MUSIC mode! was able to describe adsorption by a soil dominant in ferhydrive and allophane over most ofthe range ‘of arsenic concentrations studied. Because many parameters were fit, considerable uncertainty exists in regard tothe uniqueness of ‘the mathematical solution. Further Reading ot i and wn are (19) natn an nan etch consurs Bak et} Sal champ, yao aes, 48-80. inn Eee. at a er 8 (155) Sule conpletn wag in pn ces. sins i Mo) 217-280, om A an Mo Fah I) Se canplatan mya oe ae Ne Ye st Ve. Cer (02 Ue se cnplton made Some tre ders in Amey: 25338 (kb S19) Corset gate mo theres sata carotene rey apn oc arts on sol ils Ane ae acy ‘Syaposn Sees 1 2807 eg (1) lon a apa ko cen lum nods bmp Sut Par ot | Chace a sn mats, 137-0 sso Sox Sob See Arar. ate (108 en ake al ot pean in: oeng srt Hang PM, Snes, nd ale) UPN Stes on nls [ial chose pcm syns Sea sta cs a as, 4p. 377-412. CHC: Wl. cate a rt LE) Hes apn ors od mes yal eampaens. tra A, Hang PU, dat G(s) Bopha oe yr a en 30 eee. 215-264 Hobos Wi. iota nd Resi (22 On he etapa sf ado Compan ae salu rusk utd AT) tot ea ca ie, 3773-270 te Yo: Mace Dt, bons A and ans GA (8) Crate as cals yr ode en rss heal pees, St a Call Scr "2-1-1216 Sento 6 (150 Foren tere enpaston recall ad aueus tn Mb, ef Ca tie S220. Sst (0 he sare ris o sas. Ox Oed Ue Press Feerence Module in Earth Systams and Environmental Sconces, (2018)