The characteristic of chemical elements condition in underground waters of the river katun basin (mountainous altai) is shown; the main forms of migration of chemical macro- and microelements are allocated: na+, mg2+, ca2+, mn2+, fe2+, pb2+, сu2+, zn2+. statistical calculations, which purpose was confirmation of results of complex-formation process modeling, are carried ou

Lokhanova, Yu. Yu.

Rasskazov, N. M.

Electronic archive of Tomsk Polytechnic University

105IntroductionForeign and domestic researchers in different yearswere engaged in researches of forms of element migration in natural waters, such as: R.M. Garrels, C.L. Krayst, S.L. Schvartsev, S.R. Kraynov, V.M. Shvets,G.B. Naumov, B.N. Ryzhenko, P.N. Linnik, B.I. Nabivanets and others. Achievements of these researchers allow us to solve problems at modeling of formation processes of underground waters structure.The purpose of the given work is allocation of themain forms of migration of a number of components inunderground waters of the river Katun basin (Mountainous Altai) in the average current.The dissolved condition of chemical elements in natural waters is extremely various. Some elements areinclined to form only rather simple compounds, others– complex associates, including with organic ligands.The basic forms of element migration depend not onlyon properties of the element (cations or anions), but also on external factors of migration (рН, Eh of the environment, active concentration of ionscomplexformators complexing compounds, etc.).S.R. Kraynov and V.M. Shvets think that «migrationof elements in underground waters in the form of complexionic and molecular associates has very important consequences. Different compounds of the same elementshave various thermodynamic parameters (free energy, factors of ionic and molecular diffusion). Therefore, the processes of mass transfer, dissolutioncrystallization, ionicexchange and other, making the basis of the process ofchemical compound formation in underground waters, it isimpossible to interpret and predict correctly without theknowledge of forms of element transfer. These forms define an opportunity and geological importance of processes, as well as their kinetics. At formation of steady complex compounds there is a displacement of equilibrium ingeochemical processes (in dissolution, desalination, precipitation and coprecipitation, sorption, ionic exchange,oxidationrestoration) towards the water phase» [1. P. 33].Physical and chemical calculations play the role of areference point at hydrogeochemical researches, theirresults can be used for a rough estimate and probabilisticforecasting of real geochemical processes. However, thesecalculations are frequently based on the analytical dataon water composition summarizing free and connectedforms of elements, which is not quite lawful at an attemptto recreate processes taking place in the real system.The material for the researches were the data obtained as a result of approbation of water objects in the region, which were carried out by employees of TomskBranch of the Institute of OilandGas Geology andGeophysics of the Siberian Branch of the Russian Academy of Sciences and employees of Tomsk PolytechnicUniversity with participation of the authors (2005).The technique of physical and chemical researches ofcomplexformation is in [1–3]. Base positions of the theory consist in the following.The socalled complex compounds are formed at interaction of ioncomplexforming agent (Me) and ligands (A) of organic or inorganic origin:MeAmmk+n=Men++mAk–.Характеристикой комплексного соединенияслужит константа устойчивости Ку –The constant of stability Ку serves as a characteristicof the complex compound –where [Men+] is molar concentration of an element withthe charge n+ in the noncomplexed form; [Ak–] is molar Addend concentration A with the charge k; [MeAmmk+n] is molar concentration of the complex compound, with the total charge mk+n.Dissociation of the complex compound, as a rule,occurs in steps under the typical scheme:Me(A)2↔MeA++A—↔Me2++2A–, therefore, both fullconstants of stability and step constants are used. Inequilibrium standard conditions (at 25 °С and 0,1 Pa)the constant of stability of the complex compound Ку isconnected with free Gibbs energy by the expressionΔG 0=–1,364.lgKу, where ΔG 0=ΣΔG 0prod.–ΣΔG 0init.Gibbs energy, calculated by such researchers asI.L. Shok, H.K. Helgeson, P.N. Linnik, B.I. Nabivanets,I.I. Volkov, G.A. Solomin, I.K. Karpov, et al. for variouscompounds, is included into the database. On the basisof Gibbs energy and the data on physical conditions ofreaction, the constants of stability of the lement complexare calculated. But quantitative parities between conditions of any present in the water elementcomplexformingagent depend not only on constants of stability ofits compounds, but also on concentration of addends. Aspecial value for complexformation is rendered by fulvic acids, since the ability to complexformation of humic and other organic acids is much weaker.ó( , )[MeA ] ,[Me ][A ]mk nmT P n k m K++ −=Hydrogeology and engineering geologyUDC 550.42:577.4 (571.1)FORMS OF CHEMICAL ELEMENTS MIGRATION IN UNDERGROUND WATERS OF THE RIVER KATUN BASIN IN ITS AVERAGE CURRENTYu.Yu. Lokhanova, N.M RasskazovTomsk Polytechnic UniversityEmail: Juliatomsk2004@rambler.ruThe characteristic of chemical elements condition in underground waters of the river Katun basin (Mountainous Altai) is shown; the mainforms of migration of chemical macroand microelements are allocated: Na+, Mg2+, Ca2+, Mn2+, Fe2+, Pb2+, Сu2+, Zn2+. Statistical calculations, which purpose was confirmation of results of complexformation process modeling, are carried out.Fig. 1. The scheme of observation points distribution: 1) observant (regime) hydrogeological wells; 2) springs andtheir numbers.Explanation to Fig. 1: р. Чемал – river Chemal; Толгоек –Tolgoek; Азотный – Azotniy; Поплавочный – Polavochniy; р. Апшуяхта – river Apshuyakhta; р. Катунь –river Katun; Дорожный – Dorozhniy; Скальный – Skalniy; Водосливный – Vodoslivniy; р. Каспа – river Kaspa;р. Чеба – river Cheba; р. Эдиган – river Edigan; Каинзаирский – Kainzairskiy; Питьевой – Pityevoy; Бельевой– Belyevoy; Большой Ороктой – Bolshoy Oroktoy;р. Н. Куюс – river N. Kuyus; Куюсский – KuyusskiyCalculation of concentrations of various forms ofelement migration in underground waters was made bymeans of the program module for PC HydrGeo (author– M.B. Bukaty, Tomsk Branch of the Institute of Oiland Gas Geology and Geophysics of the SiberianBranch of the Russian Academy of Sciences) [4].Description of the research object The basin of the average current of the river Katun(Mountainous Altai) occupies the area from the mouthof the river Koksy up to the mouth of the river Smulta.Hydrogeological conditions are defined by significantbreaks of the relief, active waterexchange and presenceof two waterbearing complexes of rocks – alluvial formations dated to valleys of the rivers, and fractured bedrocks, mainly Paleozoic, rocks that are broken by disjunctive tectonic destructions which actively influencethe course of underground waters. Waters of these infringement zones are poorly revealed and studied. Waters of fracture of bedrocks and alluvial sediments areof a great importance.Table 1. The data used in calculations on composition of underground waters of the basin of the average currentof the river Katun (based on the results of analyses ofTomsk Branch of the Institute of OilandGas Geology and Geophysics and TPU, 2005, except for CO32– –1999; Hg2+ – 2003)In this connection, the process of their chemicalcompound formation proceeds in various conditions.The module of the underground flow amounts to3,2...4,0 l/s.km2 in the region. The afflux is within the limits of 0,1...0,4 km3/year [5]. The interval of approbation in wells mainly amounts to 100 m from daily surface (the maximal depth of of wells is 160 m).Underground waters of the considered territory arefresh with mineralization of 70...700 mg/l, as a rule,neutral or weakly alkaline (рН 7,0...8,8); in structurethey are hydrocarbonate sulfate. More detailed characteristic of geologichydrogeological conditions and geochemistry of underground waters of the basin of theaverage current of the river Katun is given in publications [6–9].The results of researches of migration forms of themain macro and microcomponents, especially carefully normalized without taking into account elementorganic forms, are stated in the given work. The scheme ofdistribution of approbation points is shown on Fig. 1;initial data for calculations – in table 1, calculation results are presented in table 2.ParameterMeasurementunitPoints of sampling – springsTolgoekDorozhniySkalniyKainzairskiyPityevoyKuyusskiy 1 2 3 4 5 6рН 7,9 7,8 7,7 7,7 7,6 8Ionic force mol/l 0,01 0,01 0,01 0,01 0,01 0,01Mineralizationmg/l360,0 350,0 390,0 290,0 370,0 290,0Na+ 3,50 4,00 7,00 0,80 8,00 5,00Ca2+ 44,0 56,0 60,0 60,0 72,0 52,0Mg2+ 9,80 20,70 25,60 12,20 9,80 10,50K+ 1,50 1,10 1,20 1,50 0,80 0,90Fe2+ 0,8 0,01 0,05 0,08 0,07 0,03Fe3+ 2 0,1 0,02 0,02 0,02 0,02Mn2+ 68,70 18,60 20,40 12,00 10,40 12,70NH4+ 0,10 0,08 0,10 0,10 0,07 0,06Al3+ 0,25 0,25 0,25 0,25 0,25 0,25Cl– 1,56 1,42 1,42 3,55 2,84 1,28HCO3– 268,4 292,8 366,0 268,4 329,4 244,0F– 0,15 0,12 0,56 0,10 0,22 0,18NO2– 0,39 0,01 0,01 0,01 0,01 0,01NO3– 4,03 3,33 5,90 17,24 16,91 3,25SiO2– 3,70 3,70 3,35 4,15 4,15 4,80CO32– 0,4 1,2 0,4 0,6 0,4 0,4Pb2+mkg/l2,73 1,25 1,09 0,46 – 0,17Cu2+ 10,6 1,98 3,28 0,75 – 0,03Cd2+ 0,11 0,1 0,09 0,03 – 0,07Li+ 9,00 7,00 9,00 8,00 – 9,00Zn2+ 29,2 49,3 26,7 0,7 – 1,93Hg2+ 0,002 0,002 0,001 0,003 – 0,001?.??????.???????.?????????.??????.?????.???????.?.??????????????????1 2 3??????????????????????????????????????14011404??????????????????????????????140814054 56 7????????1.5 1.50 3.0??C??.??????????????????1 21403106Bulletin of the Томsк Pоlytеchnic University. 2007. V. 311. № 1107Results of physicalchemical calculationsTable 2 shows calculations of complexformation inwaters of the tested regime springs which allow drawingthe following conclusions.Table 2. Calculation results of the basic forms of microcomponent migration in underground waters, %Note: mg/l is the content of the component form in water, number in the denominator – %, falling on this content in waterWithout taking into account compounds with organic radicals, mainly in the ionic form, ions Na, К, Ca,Mg, Cl, HCO3, F, NO2, NO3, HCO3, Fe and Mn migrate. They share makes, as a rule, more than 90 %, whichis quite natural, considering nearneutral рН values ofwaters, oxidizing geochemical condition, low mineralization of solutions and low values of their ionic force(0,01...0,02).Among the forms of microelement migration (table 2) complexesassociates with participation of dominating anions HCO3–, CO32– prevail; occasionally thereare compounds with Cl– and F–. Hydrooxidic migrationforms are more characteristic for elementshydrolyzates: H4SiO4 is the basic form of migration Si4+ (morethan 50 %).At the same time, practically unique migratory formfor Al is products of dissociation Al (AlO2– иAlO(OH)2–), since concentrations of Al are so small,that they are insufficient for formation of weakly solublehydrooxides Al3+, AlOH2+ or AlO(OH)3. Si, containingin waters of Katunskiy range in quantities close to maximum permissible, is in the form of two basic forms ofmigration – dominating – H4SiO4 and subordinated –SiO2, in quantity of 52 and 48 % respectively.Based on calcualtion results, the basic migrationforms for Mn were Mn2+ (more than 70 %), as well asMnHCO3+, MnCO30 and Mn(HCO3)2.A little bit different forms of migration are characteristic for Fe. In the given geochemical conditions, thebasic form of Fe migration is Fe(OH)2+ (more than68 %), and secondary are Fe(OH)30 , Fe(OH)2+,Fe(OH)4–. From compounds of Fe bivalent, the ion Fe2+prevails, its secondary forms are FeHCO3+, FeCO30,Fe(HCO3)2.CaCl2 0,00 0,00 0,00 0,00 0,00 0,00CaF+ 0,01 0,36 0,01 0,01 0,00 0,00Mn2+ 48,1170,0314,4577,6715,5376,339,7481,198,0377,1710,1880,19(MnHCO3)+ 0,01 0,00 11,89 9,50 11,49 9,99MnCO3 0,01 0,00 10,74 8,69 10,39 9,15Mn(HCO3)2 0,00 0,00 0,99 0,57 0,92 0,64(MnCl)+ 0,00 0,00 0,00 0,00 0,00 0,00MnCl2 0,00 0,00 0,00 0,00 0,00 0,00MnOH+ 0,00  0,03 0,03 0,03 0,03Fe2+ 0,7290,560,00994,660,0594,260,07695,630,06694,510,02995,37(FeHCO3)+ 0,04 0,00 2,89 2,21 2,77 2,34FeCO3 0,03 0,00 2,09 1,62 2,09 1,72Fe(HCO3)2 0,01 0,00 0,49 0,27 0,44 0,30FeCl+ 0,00 0,00 0,00 0,00 0,00 0,00FeOH+ 0,00  0,25 0,27 0,25 0,27Fe3+ 0,00 0,00 0,00 0,00 0,00 0,00(FeOH)2+ 6,23 4,79 3,26 2,80 2,82 3,06(Fe(OH)2)+1,4170,410,06868,210,01471,230,01888,860,01678,910,00280,30Fe(OH)3 23,32 26,90 25,26 8,02 17,96 16,48(Fe(OH)4)– 0,10 0,19 0,35 0,43 0,43 0,29MigrationformsSampling points1 2 3 4 5 6NH4+0,0995,050,0790,190,0993,760,0995,100,0689,890,0591,38NH4HCO3 0,00 0,00 0,26 0,19 0,24 0,19NH4CO3– 0,00 0,00 0,00 0,00 0,00 0,00NH4Cl 0,00 0,00 0,00 0,00 0,00 0,00NH4OH 0,00  0,39 0,41 0,38 0,39(NH4)2CO3 0,01 0,00 5,19 3,89 9,10 7,64NH30 0,00  0,39 0,41 0,38 0,39NO2–03999,860,00999,860,00999,870,00999,860,00999,870,00999,86HNO2 0,00 0,13    Mg2+ 9,1192,9720,0796,9624,7596,6811,997,569,4996,9210,2397,41MgHCO3+ 1,33 0,56 3,07 2,27 2,87 2,42MgCO3 0,05 0,02 0,10 0,08 0,09 0,08MgCl+ 0,00 0,00 0,00 0,00 0,00 0,00Mg(HCO3)2 0,06 0,03 0,09 0,05 0,09 0,06MgCl2 0,00 0,00 0,00 0,00 0,00 0,00MgF+ 0,00 1,15 0,04 0,03 0,02 0,01MgOH+ 0,00  0,00 0,00 0,00 0,00Na+ 3,4598,583,9899,436,9699,370,7999,547,9599,404,9899,52NaHCO3 0,37 0,07 0,61 0,44 0,59 0,47NaCl 0,00 0,01 0,00 0,00 0,00 0,00NaH3SiO4 0,00 0,00 0,00 0,00 0,00 0,00NaHSiO3 0,00 0,01 0,00 0,00 0,00 0,00Al3+ 0,00 0,00 0,00 0,00 0,00 0,00(AlO2)–0,2496,640,25100,000,2392,890,2392,820,2392,880,2392,82Al(OH)3 0,00 0,00 0,00 0,00 0,00 0,00(AlO(OH)2)– 3,6 0,00 7,11 7,18 7,12 7,17SiO21,8148,911,8148,911,6448,912,0348,912,0348,912,3548,91(H3SiO4)– 0,11 0,11 0,11 0,11 0,11 0,11H4SiO4 50,84 50,84 50,84 50,84 50,84 50,84(HSiO3)– 0,13 0,12 0,13 0,13 0,13 0,13K+ 1,3791,711,0999,411,1999,361,4999,540,7999,390,8999,51KHCO3 0,03 0,00 0,63 0,46 0,60 0,48KCO3 0,00 0,00 0,00 0,00 0,01 0,00KCl 0,00 0,00 0,00 0,00 0,00 0,00K2CO3 0,00 0,00 0,00 0,00 0,00 0,00Ca2+ 42,4996,5654,1196,6257,7396,2258,3497,2469,4196,3950,4697,04CaHCO3+ 2,98 0,85 3,28 2,45 3,20 2,61CaCO3 0,22 0,06 0,24 0,18 0,23 0,19 Ca(HCO3)2 0,15 0,08 0,18 0,09 0,17 0,11Ca(CO3)22– 0,00 0,00 0,00 0,00 0,00 0,00CaNO3+ 0,08  0,07 0,02  0,03CaCl+ 0,01 0,04 0,00 0,00 0,00 0,00Hydrogeology and engineering geology108Presented on Fig. 2 calculation results of the basicforms of microcomponent migration in waters of the basin of the river Katun, show that dominating in the solution are hydrocarbonate and carbonatecomplexeswith ions Li, Cu, Zn, Cd and Pb.Group ОН gives secondary complexes Pb, Zn, Cuand Cd by way of reduction of the role of the given complex with the named elements, but on average the role ofthese complexes does not exceed 1...2 % in case of Zn,and 20...40 % in case of Pb.Complexes of Hg migration, calculated by us, specify the prevailing role methylated mercury (Hg(NH3)2)2+– cation hydrargium diammonium). It is obvious, thaton the share Hg(NH3)2+ (cation hydrargium diammonium) of mercury there is no more than 1 % from its totalquantity in the solution.It is necessary to note that not considered by us interactions of ions of the solution with organic compounds can also influence both formation of element migration forms, and on processes mineralformation.Another consequence of the presence of organic substances in the solution is primary linkage of microelements, while Ca2+ and Mg2+ form very weak compounds.Fulvic acids are bound into strong organiccomplexesfrom 0,0n up to 50 % of microelement content (especially Сd2+). The minimal degree of ion linkage is characteristic for Li+ and Zn2+ (0,0n %, Fig. 2, г, д), while fulviccomplexes are capable to link from 0,0 up to 16 % fromthe initial quantity of cations Pb2+ and Cu2+ (Fig. 2, а, б).And, at last, the maximal degree of connection is characteristic for Сd2+, reaching from 3 up to 60 % (Fig. 2).Basic conclusionsComponents Ca, Na, K, Mg, Fe, Cl and F migratemainly in the ionic form composing 95...99 % from theirtotal ammount. Among various forms of migration ofsuch elements or compounds as Mn and NH4, the ionicform takes up only up to 80...95 %; for Cd, Pb – only5...40 %, and for Cu, Zn and Li it takes up from 99...76 %.The maximal values of adhesiveness with fulvic acids arecharacteristic for Cd (3...60 %). At hydrogeochemical researches, it is necessary to consider the level of elementadhesiveness in strong complex compounds, since the level of their adhesiveness noticeably affects the processes ofmigration, sorbtion, oxidationrestoration of elements orprecipitationdissolution of their compounds.Bulletin of the Томsк Pоlytеchnic University. 2007. V. 311. № 1Fig. 2. Calculation results of the basic forms of microcomponent migration0 %1 0 0 %1 2 3 4 6P bH C O 3 +P b Ф КP b O H +P b (H C O 3 )2P b C O 3P b 2 +5 1 2 3 4 6CuФКCu (CO3)22-Cu (HCO3)2CuCO3CuHCO3+Cu 2+1 2 3 4 6LiФК-LiCO3LiHCO3Li+1 2 3 4 6ZnФКZn (CO3)22-Zn (HCO3)2ZnCO3(ZnHCO3)+Zn2+0%1 0 0%1 2 3 4 6C dC lC d Ф К -C d (C O 3 )2 2 -C d C O 3C d H C O 3C d 2 +а бв г д5 5 55bHCO3+bOH+b(HCO )3 2bCO32+CuHCO3+Cu(HCO)3 2LiCO32+CuCu(CO )3 22-LiHCO3+LiCuCO3HCO3( )3 22+dClCO32-ZnH 3+O3 22+)3 22-n O3109REFERENCES1. Kraynov S.R., Shvets V.M. Geochemistry of economicdrinkingpurpose underground waters. – Moscow: Nedra, 1987. – 237 p.2. Garrels R.M., Krayst C.L. Solution, minerals, equilibriums. – Moscow: Mir, 1968. – 368 p.3. Linnik P.N., Nabivanets B.I. Form of metal migration in fresh superficial waters. – Leningrad: Gidrometeoizdat, 1986. – 272 p.4. Bukaty M.B. Geoinformation systems and mathematical modeling.– Tomsk: Publishing house of TPU, 2002. – 75 p.5. Shvartsev S.L., Vorotnikov B.A., Kuskovskiy V.S. et al. Hydrogeochemical conditions of the river Katun basin in the influence zoneof a projected water basin // The Katun project: problems of examination: Materials to the scientific conference on April, 13–14, 1990– Novosibirsk, 1990. – V. 1. – P. 62–63.6. Shvartsev S.L., Kuskovskiy V.S., Savichev O.G., Kopylova Yu.G.,Lukin A.A., Domrocheva E.V. Ecologic condition of undergroundwaters of the river Katun basin, used for economicdrinking purposes // Tendencies and development prospects of hydrogeology andengineering geology in conditions of market economy of Russia. VITolstikhinskie readings: Theses of reports of the scientificmethodological conference. / SPbGI (TU). – Saint Petersburg, 1999. –P. 135–140.7. Katun: Ecogeochemistry of mercury / Edited by N.A. Roslyakov,V.S. Kuskovskiy, G.V. Nesterenko, S.L. Shvartsev, et al. – Novosibirsk: Publishing house of the Siberian Branch of the Russian Academy of Sciences, 1992. – 180 p.8. Lokhanova Yu.Yu., Rasskazov N.M. Geochemistry of natural watersof the river Katun basin in its average current // Bulletin of theTomsk Polytechnic University. – 2006. – V. 309. – № 6. – P. 32–37.9. Schvartsev S.L. Hydrogeochemistry of the hypergenesis zone. – Issue 2, corr. and add. – Moscow: Nedra, 1998. – 366 p.10. Kopylova Ju.G. Organic substance in underground waters of mountain areas of the southeast of the Western Siberia and studying of theinfluence of organic acids on migration of chemical elements in waters. – Tomsk: Publishing house of TPI, 1984. – 49 p.Received on 20.12.2006Hydrogeology and engineering geology

Forms of chemical elements migration in underground waters of the river Katun basin in its average current

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