INTERNATIONAL GROUNDWATER SYMPOSIUM ON HYDROGEOLOGY OF COLD AND TEMPERATE CLIMATES ‘D HYDROGEOLOGY OF MINERALIZED ZONES PROCEEDINGS Editor: C.L. Lin Halifax, Nova Scotia, Canada May 1-5, 1988 Sponsored by ATLANTIC CANADA REGION The Intemational Association of Hydrogeologists Canadian National ChapterA CRITICAL EXAMINATION OF THE CONDITION OF BLECTRONEUTRALITY IN GROUNDWATER Kevin A. Morin Morwijk Enterprises Suite 1706L, Laurier House, 1600 Beach Avenue, Vancouver, British Columbia B6G 1¥6 canada Paper presented at the International Groundwater Symposium of the International Association of Hydrogeologists, Canadian National Chapter, Atlantic Region, Halifax, Nova Scotia, May 1-5, 1988 157Noraijh Bterpeiees suite 1706b,. Laurier House, ‘600 fen verte, vancower, sritian alurbia ‘Gress ‘tho evaluation of overall analytical accimey of grombater chenistry 1s oftan nade throug the elactronedtrality equstion, which regiires the equivalents of catiore in a unt mss or voluw of solution equal thee of Grins. hie (opie ehat electromraliey ie a characteristic property, Of grumater, there area rimber of argments for the existance of Slectrenatralty, is oe widemprand reports of electronsitrallty (Within Gratytical accuracy) “and the Vetid” application ef reversible Ghenmodyranics, aa well as arguments ogainst it, such as. sorgeion, toh exchang®, and ‘radioactive decay.” presentimy’ these arguments ahd by. Sxamining the current views in hydrojeolory cn the datin.tion of eystens Redon scales of ommimvion, this paper leds to the conclusion that Slecarnautesisty (f not a thworetical # priori coiition of gramaater, Sut ie a commonly chacvad congition within erwlyeical ssmiraey, Juthor's Note: Through peer review, I have been told that the condition of fipaaneneal chercal property inser, a Giscrepancy in the geologic Pfteracure apparently exists and indicates either) ‘cloctronoutrality is not a furlanereal property Lt an coc ayetar, (2) aNpoer review of thin paper and my tesponse Sevariiny several detalles facie camot he fnchated hore Put aye available Woon reqoest In the reais of ion-pairing theory, dissolved solids in groundwater posoass both chanical and electrical properties. An integrated charo- ‘Slecerioal view of cations and anions Lends to a camenly employed equation for evaluating the overall accuracy of catienanion analyses, he Sleceroneutrality equation. One fom of the equation Is TGR = ((CATHAIG/ (CATVAK) | 3 008 a ‘Soore! CAT = oun of all cations in mil}laivatente/1iter ‘BN = gum of all anions. in nllliequivalente/{ sear Milllequivalants aro cbtained by muitiplying the mater of mliLisoles per Liter of each ion by the absolute value of each spaciea* Lone charge, Te sagen" Gh pgation 1 laplics the \ater sample is theoretically ‘cieceroneutial or Nchaige balsa” Xt is surprising how rigidly this equation is exployad in Light of the ide scneptance of the porwideal, ceale-depandert, stochastic metres of Sther “syaregslogic canexpes sich ae Hyurmulsecantoctivity,disparsicn fed aiffasien. Assitieenlly, a higher or lover E:R0R will be cbtainad from epcciaead water analysis relative to the unspeciated water analyals. in Grier to question the Senmope of charge balance in geammater, this pape (Sarina: arpments for and aquinst the expectation of electroneutrel ty Because Us vaiidity of the arpmmnts ste atnaitive to the scale an to the Geriniticn of a hytenjeclogie system, an initial discussion of sole. aii ‘pyotan vill (be presented and later expand in the arguments 2, SALE RERUREY ND BENETTON OF SUSIE one are extremely seal] entities, japerecirately 6x10#%/mi21inole) ard 4 Liver of water contains rouidy Jxd02 molecules of 100 and lone. If one fon ie isolated ‘In ar ineginary loos! tox, tenet defining @ closed Syston, hen elactrencutral ity doce not exiet in\the syeten. Tf the systen iS expanod to dnchue 1 iuitiiter of solution (wear and sone), there ie apparently no theoretical priori naason for elecerenmutrality 9 exist sf the oystan.” Forhape 10 1ears, for eample, mace be talmn as the eysten in croer to assure the cistance of milk elesronatraliey A Surther Alsaussion ef thie point through statistical meaanics, viet is the Encis fof therwlynanice, ‘ie prosanted ina later section. he this point, the Preceding discussion lekds to tw important complications: ‘he first complication Je tat the sanale of examination" say not coincide with the Seale of the Sjsten.” Av example can best explain the Gistinction (Gaveye and Spooito, 198e, “and Ostman,” 1986, provides Sathemtical ‘diseission). If 100 Iitars of graschater ‘solution. 42 Papiired to attain bulk electrunautrality ax this 100 Lieare i dogs! as 2 Closat ‘system, then the Teneval of a 1 L sample for amlyois may et Provide an electrewmtral sawple. ‘In this eanple, tie sone of amination (the 1 Titer eaeple) daos not coincide with the scale of the electronettral system. In samo cases, the scale of coamination ie sinned toldefine the scale of te ayeran‘he sonond and nore formidable corptication is the valid definition of a nydrogeologic systan where the mole aguas frase isin intite ones ith “elatvely "etatierary ‘paras sola pase * in me geochenistry, a cyotm can simply bee dafing’ as a guntity of solid and [ES aseociatad poraeatar. In chauieal hypdvogeolayy, if 2 system Le defied on the basis of a quantity of solid, than gramhater of charging chemical Smqocition on cme tine scale is cmstarely entering, interaction) with, far leaving the gst. On the ether hard, if a hyurayeolagic eysten is Gotinad on the basis of a quantity of grandiater solution, then the porsis SSLi2 phase of changing chnical Gonpositien (nicrocteata to formaticto) is Scnetantly entering, interacting with, and leaving the systan. IN other sords, pure goochenistry provides a closed gysten of immeblle phasce Sherais byeirogeology can only provide open eyetan (e-9., Marie, 1992) tae Le" atracuat by cutside proctatex unich nove Wanash ‘che syst and allow the ‘accumilatioryioee of matter aa enorgy in the eystan. Te 10 the epen ‘systars that could allow the ssamilation of charge inbalance, as expiaiced Sn’ the folloving sectien, Frew oes cceeeta of scale an eyman, the axwiments for ant inst lectronmutralley in growaater can now be precanted, he Sigaente against electrcreutallcy are presented flict thfaagh theoretical ani appli’ cases, wulchdray on pany areas of geolony Bush at Geochmistry, Dorendle geephysies, ard radioactive decay, althaush eae of the arguments allow only’ nagiigible charge iaimlaeee (action 3-5)" ‘Aithougt an sisal Gryetal of a mineral way Mave mo net elactrical istolenen, Teal ciystals (and ssorphous minarale) ‘can have a et charge becuse of crystal perfection i ‘niietiortien in the crystal Structure, ard irrogilar, broker! surfaces. Ar clestrical charge atthe Surface ie “detectable and acoumts for the’ gacchanical ‘reaceicrs ‘of Sorption and fon exchinge.(Saction 3.2). Upan dlecolution of 3 eryaeal (2) ¢ Sn originlly elaceroncutrsl, undaceatirtad soluticn will take cx the et Sarge of thd Grystal c) During precipitation fron an electroneutral graumtater solution, 9 crystal can dovolop lattice imperfections and inorporate foreigh Lore fro Solution. through ‘co-precipitation. Aa well, yseaia grow fot throu Sccasional aalitlons Of entire elactronautral ‘tects onto tie surface, tat through continous spiral ot irregular planes. In thea says, an electrically helance! crystal can davelop. correspondingly, any charge Sebolance in'the cystel rents in an equal, but omesitaly chargah, Snbalance in the solution. an cbaervation cin be Soke here that "the gonbination ‘of the Liquid and solid. phased at’ this point ‘represents 2 electroneutral system, but this obeatvation “ia ‘of Tuttle Myaroyeclogic elevence for too reasons. Piret, in Nptrayoolony, the equacus pase 1s amlyzat etther indepanaant ‘of or “ewhaling te eolid Hace, thereby leading to the requirement of = ubalanced agucaus analysis Seconds the Gauyed Grourmater “will flow euay trem the eiatly., tat egpoitely. Gatyed Solids. The mgnitace of the iatalane vals depen on may ‘conti ions and ss discussed in detail in Section 2.5, in the more realistic open system of one mobile phase, charge sntolanoes could agamulace with flav. Ove Gan cwvisien aay’ related Scenavice soch as whore "an. initially” electrenaueral gramatar Drovipitatas an uraianond mineral in a stvatio beforu passing ints other Strats. Afterwards, ay uniarssturated, electronatra: grouatar flow [nea the sinaralisad ctratim and dinsclies the mineral, “in the way, the total accmuletes charge inelanoe in the: precipieacisy grouvhknter fase, hich 1s: now domgredient, will be equal to, but opposite in charge of, te (Slsconving groueoear mae aa of ‘en a relatively stable mineral, quartz for earple, Se cram! into qratier grains and thane graine are assed toa pitnaitesl cater with Gigsolved solids (ciccat eystm), seme cations. vill" cammenly be drain to ana eightiy bow ‘to the rapeively eratges surface, “TE tne bend cations Go not cmpletely rautraize the surface Guiye, « "diffuse zone" of Tore loosely ‘held cations (with sow anions dram by the concertzata cations) and polar tater soleailes will Ie near the aieface. we streah with which cation in the diffuse zone srw held near the surfooe cacresses fr the. lar bouiary to the aster bounary. he outer teusday exten Goretically to infinity, wit praceically has a Lime becuse” Sone are Giserete paroels of mace’ ant charge. the combined surface/alffise-zor jion can clain elactrneutratity, Init by racoccity creates @ net neaweive charge in tho tree (unbound) greudoter. “Altemavively, ene can say tha the solia and’ its ‘ourface rimalne charged tile the total water phase Inctuding the tightly bound cations ramint electronmtn). the ect realistic scenario fof floving Grawdsatar probably Lies beten these ta Alternatives and se diacusund belo: Tt is interesting to note that eaventially all current york on sorption (and wichange) ‘reactions. calls for electroneutral ity vin the crystal curface, bound ons, and ditfice gone are talon as a cysten (ede, Saree and fares, 1002) “while the reswtig, Urblaneed ‘bulk enter iS lignered.” On the ‘other “han, ‘eacentially “all Guster wock on aqueous rections implies clectronaitrality in the tater. iin tose tie areas of Fesearth are combined, as 1g often required for hyiseyeolayy, there ariees eo qlesticrs: (3) share is the Boudry betwen the scfid and Ligeia Phases and (2) whlch phaso, if ary, cas claim electronmiraliey., Tes Shestions will bo adireatad as clarifying detalts ase presenta, Te simple scentrio of adsorption presented above is not represeriuative of mast gramdscter ‘ayrteme, ist chich the “grain surfaces fave buen in contact vith water for long petiods of tise,” dn nxt cases, bound "iotw and diffuse eonas fave previously seamilatad ant can only bo penitied by ion excharye, Throw fen exchatge with establ land mirfacor, Seas cation Ste erties for te atta cation, ‘ad curfoce Shes my conurently release Hf or at or undergo other alteration © Fetain reaction elactraneten ity,sintlar to adsorption reactions, rating in varying imbalances sm each frase, These reactions are referred to aa Minknlenced cchwepe reactions" Tithis paper. the @animtion of these wibalanced ion-exchange and adsorption reactions on the lovel ‘where the Wik water and solid matrix are tala Gre gyotan my initially ‘cause Little concem because the. cenblned Groundater ant solid satebx apparently still retain the cane het char. ih the open sjatens of yrojeciosy, thoosh, Grauwatar flow carries the Groumiter suey Crus tin change sites ard, this, che of both separated Pisce can carry a Pet charge, aharefore,, iol anmwer eo the agoronen ict! Spaseion of wan fee Gn cin tn lacunar, acme fe nates finse io naessarlly clactruneutral whan the Uablanad Fractions operate, no matter uhere the nauxiary betiean the cold. a Tigaid phases 1s" lontad. The answer for onchalona when electrically Tulaaad en, escange secure" eacage/ecrption actions operate Test Tequliras a clasar look at the aiffuse sone. ‘the bound ions on a crystal curface can be thought of az part of the crystal beonuse of tha strony bonds with @he exchange elves, avchough the busing ean altertatively be Viewed as a coneinam with the’ diffise tone fr any cise, the diffuse zone le more of an electrostatic effect, where the Stoength of attraction dacmmases With distance fran the surtece. the outer fortlun of the aiffice zone will be owpt aay (cheated) as grouroter Wow (esd. Woeloen ct alee 1906), ‘epends ‘nthe enesuy expended by the groweatar! for eample, the greater the velocity. the greater the width of the diffuse zone that Se. cheated my. convaqantly, the penctical betwoon the meblie equacus hate ant the relatively imebiie sol{d phase’ Lies somechare in the Gifhise Eons ait likely 1s. dependent on Ohe velocity of the saver ad the cscge Gensity of tho curfane. By emplaying nie reasoning, it Sypeas eae elactrencutral growehaver probably renmine electronectral “if velocity eguins cortart thrangt an area of thaarad diffuse zone while at Use san Cine ‘the rogion of solid surfaces and imebile warmed eattise zane eceuntial ly remaing electrically charged bocce of incompletion: O0 the Shar hand, “If valceity decredeas of increasce “in tearsicrt oysten, Charge inbstance sauld develop in” the er ana could decrees OF Increaca, respectively, in the sarfaee/@ittine tone region. his erfect Can eocut in Tespanse £ bot natura) eeanetent. distdir and nrtificial Gisvurbanoes ‘san as pp wets and grommater sampling, feerinle ruupitoroe of lnbalanaas are adireceal in Section 4-5, 2.2 Mochanians Of pittusion end Dispersion Tn diffusior-deminated situations, ren-aquil brio conditions prevail (hao, 1986) and charge balances. can “aovelop because the diffalon Gpetticient for each ionic spacias. io sligeely different. Tis, in low permaability strata, charge Inpalances could develop over lorm periods of Eine. On’ the other hari, in. Gispeseion-diminated situations, change eholances canct develop in'a similar fashicn az Siffasion becnuse Current theory attributes dispersion to velocity apd dispersivity, iniepensert of the thigue behavior of different lone spaces. Ie is intrigim to considar opecies depersant dispermion® however, this seald enly ai te the Presently precariaus siumtion (Spoctte ee as, 1986) because dispersion represents a gradutl mixing of to of more mses of water, 2 deterministic view of deparsion ineiestaa an electronetra) Water would result fron the mising of tio electroneutral water or, Py Ghiree, frum the mbuing two water maves of Sactly opposite. inbalarons Sh adiition,. the being of an whelarood water ant an electroneutral water sould reat in an Untalanoed water class to electeonaitest ity 24 Mechanism Of. Radioactive Decay fo an atan projrescively aacays through a decay series, its cheno electrical’ propystion including valence vary.” for gamle, the Upper ont Pf, dny, sare, acre hy tgplwing, trae clane for SEG atcae Baya SSSR, EG, emotes $2, So} ving, Seaneisigns for = Bond, zebde nace of the variation, an clocctonmseral ey entalning anty Ont gs Gost ing 12 nlilisolar ratio, for expe, iL eventually contain Sau and cther daughter predicts and 50q2 in [2 millimolar ratio." Rurthersire, radionive decay in effect ‘creates ome matter from a geochenical viewpoint by ejecting alfa particles, ich sre ecsertially heliim mclel without’ shell electrons, and. bet Farticles, sfuicn are escontially electrons. The alpha particles can tecure the heliim atone often found in Fedicace/ve arene by capturing elections fran’ anelis of other ions, i.e. ty inereteine lon alae Camis rome positive values, and the beta particles can Yow the welenr of lon Eras nore negative values spon shell capeite, "in test ways, a chasse SHbalanoe can accrue ina radioncrive hydrageologic system, 2e5_fussible MeanStixes Of Inbalance Develops my The Aforemant fone! ‘echanton ofore proceading to published pachanions for charge Srblances, it is inceroctive ‘at Uus point to Gaming the nagnitide of irkalance that horal precipitatien-dissalutien, sorption and ion exchange, diffusion, Se aimee desy con praise for sizple illustrative purpooss, the magnitude of charye inbalance in 2 minaral cnieryoing precipitaticrdissclution (action Nl) te. touhy approximated by the ation Capacity (exe) of the mineral alehingh Wie clear wae crystallagrephic teatuine such a coordination and auteiae variations. ash ag” in agusour gi can modify the Ge valuc and thee doe Intarnal crystal inbalancar mate 4 velntive:y sinor caitributicn to CB Gor "values. in grounchater generally vary fre approsirately 0-1 9.100 ilLiegiivalents/109 g of mineral, ing that change intalanccs ‘ot Srpronimealy 10° ‘to 1 miitieguvalentyliter could develop upon Procipitationdiscolution of @ muierately soluble mineral (abut I’ g/t cr Fougily 1-10 nilimoles/t). The precise dagree of balance wil’ depth oo Such factors as the Solubility, Fatio of ceystal surface to voli (grein we. grain costing), solution campasitien, jonic strength, and resection Kinetics.” many) Caso, the ability ta practically detec this. irmaisnoe Choagn a water aralyeic and Byation 1 Gopents cn the total mimber of milliequivalents/t in’ colution. "Fore maderste grouxteoter vith severn) sallienivelente/t, “the chasge isbalanae will be tess than analytical Somurecy a, th) not dotacable, ‘he general nagitude of ary change Lnbalance resultiog frm sory ion for ton exchange can be inferred trom the sounatio developed in sacticn 2 Por‘ the grauuhater mas hich first contacts @ fresh surfaoe (eine‘gdsorption), the squenis balance wlll reflect the CHC as 9 maxima Limit, na stratun with a porosity of 0.40 anda matrix dawity of 2.7, 1 Liter (of Grourtvater will be in contact with «050 g of motrix. bith @ generally choerved Gx range of 0.1 to 100 nag/200 g, an ishalance of 4.05 to 4050 ec/ could onaur, “Coviowsly, the higher’ isbatances carmot davelop in 1 Titar of moot graumhmtars bacadsa of Lack of sufficient. dissolved ool ide (4050 neq/L). “Tiawver, the higher inbalances sugsest that, alvarnatively, pany Ltars of gromstar could be atfectaa by efty 100 9 Of axttbe, BIN Blew Cpe material coule Somonivably cause a eigiificant acamilation of Charge imbalance with tim, because’ ope Liter of fasta ing gromibter thrash the lov cer mavariai could socmilate a sindlar dagiee of inbalanoe ina unit of tine as elownoving qrouviatar threo high GO= material, Por grountoter mases subjected to urbslanosd ion exchange reactions, the Labalanen can at Tost be equivalent to the above sorption valves. FOr gramater weergoiny balanced exsunge of 70 Liguid-aciia. interaction, the water will raintain ite original chuge i velocity remains constant Xf velocity decreases at a location, 9 tee negative lstwlait may develop by hat lent of cations to te incmplete dignise zone, fait this loss will be najligible caparat to the CPe-base! valves. Por dinasion (section 3.3), the possible magnitude of inbalance is ependent ‘on the differen beter trividual difeonicn coetCicierta,, the feriginl concentrations, ant the length of tine of ‘diffusive tovemant ‘Tus, the mina magnutiate ix Uyeoretically high. Sinlarly. the possible ange of inzalanoe caused by raionctive decay (Section 3.3) 1s dependent on cviginat coneertrations, leecth of time for decy’ relative t> Tadiomucl de nai¢-lives, and the sauce of elewonte formed hauye inbalanse as dovelopad in the previous sections is cosod by the celationship of mass and enargy in fonic aiamlved solide. If a change Inbalanee develope in an electroneutral water, chery must be oe, hth alto separ potential weigy et ip avaiiavie % @ ork! “Trerefore, a chage inbalanee im groueater represents & potential Chat mst he contidared shar evaluating all other potentials (e.g. araviey, Bresaiie, Ghenical, cenotic) ‘wo define grauvnater movment afd chnictsy. Iie will be discussed Auther in Section “The preview sactions have dissisead thos teoy the coon reactions ‘that can ‘lead to urge inoalanoes in gramhater, alto @egerinental evidence for’ the istelance an grouihster thecady tece Fesctions “is “gemraliy lacking. However,” evisanoe of imbalances ie Feported. (often indirectly) for more dramatic aivaneions, expecially ion fiteation "in "highly cmpacted ‘clays and cley-rich stiatay artificial Gesal ination, "spacitic Gonmaccance neamurenents, int SP torehole tose len clay és highty compacted, the positively charged diffuse zones en cepecite surfaces of a. pore are close toy oF achieve, overlappire, This SERS Sh Sesleri "otras se (Oe! pitonly ya etuse snes electrically repel cations attempting to Flew past then ar (2) Wie diguse zones attract agucous anions (0.9. Rosraka and tarry, 19737 Bresler, 1973; Besler ard Laufer, 1974). tse differential attractions fn reptdsions, which can bo graged unter “lon filtration, cay Fesate in 4 cunge fabalanae in grombater (e.g, Frick ot al., 1976) Ina eupension (ster and muqenied charged particles), the electrical ciarye of the particles is inom eo dinmpe electrically’ based soasurements such ae pil (eg- Limet, 1970). A mimpension presenta. an Srearesting- deviation ‘ram Section 3.3 ip that the carged surtaous ae Produce deflections at litholoyic eartacer (eng. Sanlinbenger Wed. 1872) he jon-flitration capacity of shales reporterly alloe only the novenent of cations to the berebale, recultinj in charge inbalarose across a Mesa hich in UN prodices 9 "nebrane potential" (Schlumbergar itd.) Tis Feportadly minor (Graf, 1983) : A detailed laboratory study of chemo-electrical Belavior of ions in Grountaiter hie boon recently renoread (Runnels ard Larson, 1506)- tp thie Study, platiram electrodes ware Placed st Poth ens of a Golwen containing Gurui-feldsper sand ard Old, solution. "When a yoltage betas 2,2 an E'S V be ws impocad on the’ clectraies, the Gi?” nigeatad tamaris the agatively "charged cathode and was elactrochenically” tedsced onto the Platina tulle Soe migrated tovarae the annde. At the cathode, cation Sxcess of about 7" of total cations am anions mildieqiivatente/t) vas ckeorved and attrinstad to anwiyeical ertor in Grier’ fo maintain Glectramtralsty. "in other sections ‘of the colum, Sneluting the region near the wese, charge inbalanes wns Often les tha 8, “Nowever, in this raion naar the ane, becaune of the strong applic’ soltage, water was apparcctly being atidisad to st (enich mist hen be Fepelied fran che anaie) “and Oy gas. The i could provide: the pewded cations to cttain near electroomitiality. Seaauce” tis concept of Clectrmnigration of “lows “ani contaminants in geamwater is" shiningattention for contamination mitigation (umes ard tarson) an for Georhenical exploration (stmakin, 1965), future stuties my provide sore awledge on the davelopnene of charge isbalance in granaecer coplge sor a Rinmeal. Sinilarly, an aguecs solution of Go ‘at Al can be Enerredimanically definad ab a COURS ALO AO ‘eyetan. These Gapownts shoe’ that clectrencutrality “ia ho aa aeamption, at an Gmpicie rule, o€ therncaymamics therefore, for thermedyranics to be applisd to a aysten, the syste mst ho electronaitral. Ie is poseible thee the opposite neasonley my be Gccisionsly used in hjdeogeology- because thermedyranice can often vel ialy Geecrine grouhatar gecchenictry, Che system mst be electTonevtral. This ‘opposite Tensning is wmccoptable bectise a niner curge ialance will Pet IDisly be eafticlent to render Uiemmadynanice inplicable: fer Sey Rees mised centage spe Cther tan the preceding empirical argwent for elactronaitraity (Section #1}, thermedyeanics provides the only other” tong alumcat for Ghirye balanee in greutwater. "If Une themodyranie argmmt if ignore, then ll cther aryiments Lead to the gararal conclusion? charge inbadatce is within overall ansiytical accuracy uver Felstively noma! comitions but can bece wignificant under umusial Gonditicra, therefore, the rigid spplication of Spiation 1 in hytroyeclogy my be simply the rent of the Serer oe, ot Ghernaanicns baciae ot tha ponsinitley $e “ie Gertiuhile to wanino in detail some findamental consepes of by returning to the discunsien of seale an syaten initiated in Section 2 5. A OSSILE RESOLTION OF ARAMENIS FOR MAO AGATIET ELECIFENEIPALITY ‘the scarch for the Representative Elementary Volume (REV) Sn phypcal hydrogeslogy ie relevant to Gis svuly an ie ud here in itz eisple ‘Sroepiaal form and not aaa rigormus conmepe (Davey ard Sposito, 1954s Serkovits and borsabat, 25057 Saveye ae! Sposlto, 2605)- As a volume wile SSeetieratien ecrannds fra sar the Yue Same phn “sack oo porosity initially fluctustes then’ roaches a stendy overage valve (at the Rev), at Ohen the value agein fluctuates ao the volune increases further. ‘The beaten for_a REV for elecereneutrality can start with the Sscripesen Of systane in Section 2 of elther a stationary Wolune of porous solids with Grourouster passing thraugs It cr a stationary volume of grounatar with Ekseing porcs solids. the former system vill be aad for the fotloving ‘sed on section 3.1, an initially electronautral gramsater ts asamed to precipitate non-igaal unialinoed coystale at, this, the grousnter tecrnas egially but oppesttaly charged ana woven daresient The cueonediny eiectrowsitral groundhater” then dissolves some of the balanced cxyetala ant takes of their chatge, In Ghle euupie, Gye RY fer clactronautrallty could be defined as the “corbiration of” the Geongradiane watar, te upgradient water, “ard the upgradient solide? owver, the dovneradient water io in contact with eollds Wist maybe Charging its isbalance thrown ary of the provescas in Sactlon 3 ane these Scwrgradient solids ware possibly influeroed by the grounsater located Goon further dammension’. the "RAY for” glactronsutrality thesetore Giermlly eogwrds to ercenpacs an entire fommtion, wel entire basin, the rth, and the universe, Wille this may saund Tatler, an REY consisting Of the universe ig not_ foreign to sane aspects of pinycicr ar chemistry” Bem (185i), as quoted by Ziemelie (10ae), concliatat "exe entice wuvere fist, on a very sonurnte level, be rojarded as a single intivisible unit in eich “Separate “parte appear’ ae analisneions permiscible only. on Classical level ‘of aaciracy of deccrigeion'. “Wore relemre to this Gisaussion, statistical nedunics, which provides bulk descriptions of Systene with ah enormous musber Of particles ard is the ‘basis of Ghemmndyranics (e.g. falaccs, 1975), Teguires We wiverss az a cyscem for Ure: uepiost ionably valid appl icatich of Uurnestamice (the "hermesynanse Vinitt, e.g. section 4.7 of Balescu) Doother important aspact in the definition of a eysten for the vali application of vatiseieai mechanics Je that any syst amaller than the Ghiverse mast fave @ "nagligible” volume of Houriaty lnyesy in which Conditions vary" fren thane ie the systan'e blk volo, Ze the boaeasy Tayer io signiticare, then etatievica! metanice and themodjrasice nay oot be applicable to. the ywum. Gaochastr observe. hie. foint shen te solubility of a crystal increased az the voline of the ciyseal decreases? for oawpie, Ter (1979) oplaine the increasing ‘lability of anemia Silica at grain diapeters lass tun 10 hwenetern. Bacmse grouaenter passer Gow a poraus solid phase, e Iylrageolsgie system ean have 8relatively large bounty layer. ‘the previous two paragraphs indicate tat thermodynamics my not rmocausar ily predict te chanical energy ina eywten aller than the Universe. "this situation ie rendered nore omplax, fut nat unelvable, Shen energy tranaformtione ate allowed in the oysten. fer exnmple, the Potential eneny of Gramdvetar reprucartad by gravity (elevation Potential) is linked to the groundater's chemical potential enaigy to, Section 7.6 of Spasito, 1901) and a change in one pocantial can artes the other potential (seo also Olsen, 1905). As a sacohd example, a aifference fin salinities (cheical potential) ecrces a nenbrane proiens chenicat oarctic pressure which can olercore ‘some dayree of a Fevers, pressure: potential’ gradient. Another example is. procentad in Saction 4.2 here ‘arlationa in Kinetic gray Of aw Gin be theceticaily curt to Charge Inbalance ‘sheared diftice ayers. These evmpies provide further argument for the integrated wianination of physical and chenical aspacts of hydrogeology: *itysical and chanical hydiogeciogy shold not be Separated since the interaction betusen physical and chanical parameters Gan no, longer be ignored” (Discussion Sasaion "Nov ‘6, First GuradinyAnerican Conference on Iyetroqeolony, p.321 of Hitchon and iallick, $800). “There have bean anitial step in the direction of tinking warions form of enemy in Grombater (0.9, Marie, 1962), tt until tore work ie one if is ifticult to predict the inpact of enamy srnnetoteations on the application of themadynanice in hyarcoeslogy. Therefore, tharedynanics and the acompunyiny requinonent of glectreneutial ity are net rmsecearily applicahle to gerumdector tase on the contitions bepire’ for a valid gyetan ad on the thevrntical aot) cheered nechiniars against electroncutrality in Section a.) Hower, the “uldeeprend chenrvation of rear elactrenetrality wigan eadlytient secarery inticates hat gramaater (ths acueaus phase) often dou poet the eysten Ciaquizenente Coe thersetpmunies ant electioneitcal ity oh the current Sales Sf eraminmiticn. ‘the cusvent aampiing scales tien ploccnctess el monitor otis are oftin in the range of several nilldlites to eoverel Titare sr the scales of laboratory chanical araiysia ate in the eenge of fractions OF pll)iiiters to tundra of saiilitam. despite te sono of examination, his popor fas presenta’ sufficient argments to justify 4 nore cautions tase of Hguation in hyerogoologic stuies, denounce Many thane 99 to Rictatus van Haeavigk (Electrica Byineering, University of Waterloo) who was willing to. Spout hours in disassion, searching) for Garon ground, “in spite of aul minimal, mowieage of the eier's special zation.” Many’ thanks also go to Jah Busby (rs. Geckagial Suny, (ustin, “TX)" for hia comments on the fleet draft of thie paper, ich ere vary helpiil, ‘and for his skepticias, which adied palate 6 pie purer. "Thanks also ‘go to an anonymeus reviewar for the opporcinity to Giscise further coverai Lesune intradiont in Wiis paper. (weal eels fie the ‘This study vas eporccred by Momvijk Brterprisas to assist In the tvenoument of hytreycolosy and low Uapatature geochemistry, ‘Balescu, 1975. quilibriun And NonequtlUarium Statistical Hechantcs. ‘itley-tetersclenns, Torente. 36ap. Bovey, Pos and G-_Spito. 2954. me cperatlonal eieniticanne of se ‘Sontirinm hypcthenie In the thaory of water aevenent thrash soils an! ‘guitars. "Hater Resources Rasenten, 20, p.Spi-500. Asvoye, P., and G. Sposite. 1995. Reply. tater Rescurone Rasoarch, 21, Berkowitz, 8., and J. Reneamat. 1985, cament_on "ie _operaticn! ‘lgniticance ot tha cantina hypothasia in the mony of water ovenent throogh soils and aquifers” by P. wweye and G. 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Groenevelt. 1976, ‘Gapling ‘Penamens in’ saturated” enovionic. momenorilicnite, 7 Baperinental, "Soil Science Society of Amrica ourmal, 40, p-430-491 crt, 0. 1982, paleai-aae: Hitchon,B., ant Bt. acrican Gontesece on waltick, ede. 1924 Procendings of the First yarogectony, Hanft, Alberta, une 23° 26, Nationa hater Well Association, Worthington, al, Usa, Nee, RK. 1979, The Ghanistry of Silica. Jot Wiley and Sone, New York. cep: Vanes, R.0., and G.A. Parks. 1982. Guracterization of aquaais coltolas by “ieee “electrical auble-iayer ad intrinsic mirtace chemical Properties.” Guapter 2 (p.118-216) in Volume 12 of Surtaon and colloid Science, “eiited by E. Mtijeric.farada, YK, afl FAF. Barry. 1973, Simltanaous flow of ster ant ‘solute through “geologic nepbranes. I. Byperimantal investigation. Ccochinica ot Comchinica hota, 3, p.2877-2003. ito, Re 1996. Mrovmlan motion ant nenequilibritm statistical machanics, ‘science, 33 (uly 18), peas0-304 Linmet, Ne 1970. pH Mensurements In Theory And Hnctioe, Fadianeter A/S, ‘operiagen. 186P. Marie, Cu. 1982. on mcrascopic equations governing mitighase floy with Girhusion ami chanical weactiens in porous media. Ineemavions) Sourmal of Bryinearing Science, 20, p.odi-ese. ational ater Well Association. 1985, Grand water... Defined: A ‘Gampilation Of Terms As Oofined By the Ground Water Irkustry. 1A, Nortnington, Gi, U.8~A. Nieteen, DLR.) Hoth. van Gonuchten, ard JM. Bigmar. 1986. Water flow ant solute transport procases i the Wuaturaead zone.” Water Racoureas Research, 22, p.685-L085, Nordstrom, 0.K:, and Jb, Miner. 1905. Gecchenical Thermedynanice. The ‘enjanir/immings Piblishing corpary, Tnc., Malo Fark, cA. 47%. leon, HW. 1985, Omesis: a cause of apparent deviations fren Darcy" Yaw. canadian Gaotecinical Journal, 22, p.238-201 ‘Overbeck, J.M.6. 1959. Oonmar-E.M.P. ane suspension effect. Joumal of Golicid Selene, 8, pasos—008 Pumels, 0... and JL. arson. 1986. A laboratory staty ot eléctranigration ass ponsible field. technique for the renoial of Sontaninants fra ground water. “Grou Water honiearing Review, 6 Schlumberger Lt. 1972, toy Interpretation, Volume I-Principles. 113p. Staakin, BLM. 1985. the method of partial extraction of mtate in a ‘corstant caret electrical field for “gaxhenical exploration Sournat of Gaachanical Bplorstion, 29, p27) Sposito, 6.1982. on the murtace camplemtion medel_of the cxide-aquecus ‘solution ineertace. "J. af teileld ane Interface Seis 91, p.329 500 spocito, G: 1981, Te ‘Tharmodynanics Of Soil Solutions. oxtord University Press. 223p. Sponito, Gu, WA. Jury, and ViK. Capea. 1906, Rindanental probless in the stochateic Gomvect ion-dicpersion nodal of eolute Erancpore in aquifers Gul field soils. Water Reaouroce Reesarch, 22, p77 Ziowelis, U. 1986. Quantumrenchanical reality, consclowness ant ‘restivity. Caman Resaareh 19, pee?-€6