J. Jpn. Soc. Soil Phys. No. 3-, p.-++,**- * ****** Soil Solution Concentration Prediction of Volcanic Ash Soil upon Addition of Acid Solutions di#er in Anion Composition Kouji KAMEYAMA*, Susumu MATSUKAWA**, Tomoyasu ISHIDA** and Hidemasa KATO** * The United Graduate School of Agricultural Science, Tokyo University of Agriculture and Technology, Fuchu, Tokyo +2-2/*3, Japan ** Faculty of Agriculture, Utsunomiya University, Utsunomiya -,+2/*/, Japan Abstract The prediction method of soil solution concentration of volcanic ash soil upon repetitive addition of acid solutions that di#er in equivalent ratios of nitrate to sulfate was examined in this study. The method for prediction was composed of chemical equilibrium equation, electrical balance and conservation of mass in soil solutions. The results were summarized in the following. +) There was a tendencyof aluminum concentration upon addition of HNO - solutionupon addition of acid mixed solution including NO - and SO. upon addition of H,SO. solution with equal soil solution ph.,) The model adequatelydescribed accumulative release of basic cations. This shows it is abilityto estimate acid bu#ering capacityof cation exchange and mineral weathering. -) Concentration of monovalent anions was much higher than that of SO. upon addition of acid solutions. It was considered that monovalent anions that remain in soil solution greatly a#ected decreasing process of ph and concentration change of basic cations. Therefore, it seemed that NO -, which are di$cult to be adsorbed in soil, are a#ected the release of basic cations and ph decreasing in soil when acid rain including NO - and SO. deposited to volcanic ash soil..) The simulation results agreed well with the measured values of ph and accumulative release of basic cations. These represent the most serious e#ects of the acid deposition on the soil. Therefore, parameters used in this simulation model are useful for predicting the main e#ects of the acid deposition on the Kanto loam subsoil. Key words : acid deposition, volcanic ash soil, acid bu#ering capacity, chemical equilibrium equation, anion composition + +33-+331 - ph..2..3,** * +2-2/*3 -/2 ** -,+2/*/ -/* :
4 3-,**- NO - SO. NO -,SO. +33+ AEC NO -, SO. HNO -,H,SO. Huete and Mc Coll, +32. James and Riha, +323 ; Xu and Ji,,**+ SO. AEC +322 SO. NO - NO -,SO. NO - Kamewada, +330 ; +332 +32* NO -,SO. NO -,SO. H,SO. +332 ;,** HNO - H, SO. +332 NO -,SO. ph,** NO -,SO. ph..* Table + + Physical and chemical properties of soil ph KCl ph H,O * + CEC cmol c kg + *, cmol c kg + *, Ca Mg K Na cmol c kg + * - Cl NO - SO. Al - /40/ /40, +1410,,41, *4-+ *4,+ *4+1 *4+3 *421 *4-0 +413 * + : *, : Shollenberger * - : *.*+ M NaOH, g:+/* ml +.*0* cm, mm + + +331 +,/ /* ml,.* g +.* M-NH.Cl -* ml / +.* M-HCl *.., *., ml, +.* M-NH.OH *.., *.,, * ml + -. HCl NH.OH / *.+, *.*,, *.*+, *.**+, *.***+ M-NH.Cl -* ml / -*
: 5 + Fig. + Electric charges of soil. -* 0. / +* 1 ph Cl,NH. ph Cl NH. 2 NH., Cl 3 +.* M-NaNO - -* ml -* -*,** ml /,** ml NH.,Cl +* 3 NH.,Cl 2 NH.,Cl NH. CEC Cl AEC + +32+ CEC, AEC C NH.,Cl mol L + ph CEC AEC, /* ml,.* g *.+.0 kg kg + -/ ml +2 -* ml ph..* HNO -, H,SO. NO -, SO. ph..* NO - : SO. *.1/ : *.,/ *./* : *./* *.,/ : *.1/ -* ml +2 / ml ph *../ mm Ca, Mg, K, Na, Al Cl, NO -,SO. C * : mol L + V * : L C N :N mol L + V N :N L Vr N :N L N C N+Vr N+ C *V *C NV N N+ *.*+ M NaOH cmol c kg + Cl HNO - SO.,H,SO. NO - N C NV NC N+Vr N+ N+ cmol c kg + SO. SO. ph..* SO. : */+*. mol L + SO. ph -.* H,SO. -, ph..* HNO -, H,SO., ph p Al -, ph -.* H, SO.
6 3-,**- Table,, Chemical equations, equilibrium constants and conditions used in ion concentration prediction + Al - +.*-.+* 0 H,.-/0 Al - +..+.+* 0 H,.-1+ Al - +.,/3+* - H +.20- Al - H,OAlOH H : HNO - : :H,SO. logk/.*, Wolt, +33. Al -,H,OAlOH,,H logk3.-* Wolt, +33.,H ExBCBC,ExH logk BCH -H ExAlAl - -ExH logk AlH BC Ex ExBCExAlExH+ - CO H,OH HCO - logk1.2, Wolt, +33.. SO. cmol ckg + /,3SO. *.,,/ H *.--/ NO - Cl *.++/ NO - Cl cmol ckg +.0.1NO - Cl *.-/, H *.+./ SO. *.*+- Al - SO. AlSO. logk-.,* Wolt, +33. / + Fwcmol ckg + *.230H *..* 0 1 SO. mol : SO. AlSO. SO. SO. SO. AlSO. SO. NO - Cl mol : NO - Cl NO - Cl NO - Cl NO - Cl NO - Cl BC mol : BC BC BC BC molmol mol *.*+ p Al - Sato et al. +332 +332 Fumoto et al.,**+ Al Al -, AlOH, Al OH,AlOH -*, AlSO. / - Wolt +33. Debye- Hückel Al Al - - Al - Debye-Hückel Al - Al - p Al -, ph Al - HNO -H,SO. H,SO. SO. Al - AlSO. Al - Al - H,SO. HNO - NO -,SO. - Ca,Mg K,Na + Ca,Mg +..
: 7, HNO -, H,SO., ph-p Al - Fig., Relation between ph and p (Al - ) upon addition of HNO -, H,SO. and mixed solutions. - ph..* Fig. - Accumulative anion adsorption after addition of ph..* mixed solutions. - Al Table - Chemical equations, equilibrium constants and conditions used in evaluation of aluminum species concentrations + Al - H,OAlOH H Al -,H,OAlOH,,H Al - -H,OAlOH * --H Al - SO. AlSO. logk/.*, logk3.-* logk+..33 logk-.,* AlAl - AlOH AlOH, AlOH * -AlSO. - AlAl *.**+ Al, BC : Ca,Mg,K,Na + log CEC*.,13 ph*.-1. +og C *.,31 ph..* C++*. mol L + ph 0 CEC CEC ph +331 ph NO -, SO. ph..* NO -, SO. - NO - : SO. *./* : *./* *.,/ : *.1/ NO - NO - NO - SO. SO. NO - SO. NO -
8 3-,**- NO - SO. NO - NO - SO. NO - SO. Cl Cl NO - Cl Bolt and Bruggenwert, +32* NO -,Cl + + NO - Cl, SO. Freundlich Mesquita and Vieira e Silva,,** ph..* HNO -, H,SO., ph -.* H,SO. Bloom and Grigal +32/ +331 Helgeson et al., +32. ph..* HNO -,H,SO.,.. ph..* HNO -, H,SO., F w H Fig.. Relation between elution of basic cations and Hydrogen ion upon addition of ph..* HNO -, H,SO. and mixed solutions...+ ph, NO -, SO. ph..* ph / logk BCH, logk AlH ph ph *.- NO - :SO. *.1/ : *.,/ *./* : *./* ph BC + NO - Cl SO. NO - :SO. *.1/ : *.,/ *./* : *./* *.,/ : *.1/ / ph..* ph Fig. / Measured and predicted ph in soil solutions upon addition of ph..* mixed solutions. 0 1 2 BC + NO - Cl,SO. *.+ mmol L + NO - :SO. *.1/ : *.,/ 0 SO.
: 9 0 BC + NO - Cl SO. NO - :SO. *.1/ : *.,/ Fig. 0 Measured and predicted concentration of basic cations, monovalent anions and SO. in soil solutions. (NO - :SO. *.1/ : *.,/) 2 BC + NO - Cl SO. NO - :SO. *.,/ : *.1/ Fig. 2 Measured and predicted concentration of basic cations, monovalent anions and SO. in soil solutions. (NO - :SO. *.,/ : *.1/) 1 BC + NO - Cl SO. NO - :SO. *./* : *./* Fig. 1 Measured and predicted concentration of basic cations, monovalent anions and SO. in soil solutions. (NO - :SO. *./* : *./*) + NO - Cl SO. SO. + + ph., ph..* H, SO., SO. 3 +* SO. SO. 3 *.+ cmol ckg + SO. +* NO - :SO. *./* : *./* *.,/ : *.1/ *.** : +.** NO - :SO. *.1/ : *.,/ SO. SO. SO. SO. NO - :SO. *.1/ : *.,/ *./* : *./* *.,/ : *.1/ *.** : +.**.- 12 10 13 NO - :SO. *.1/ : *.,/ SO.
10 3-,**- NO - :SO. *.1/ : *.,/ SO. NO - NO - SO. SO. NO - SO. SO. NO - SO. / 3 Fig. 3 +* ph..* H, SO. BC Measured and predicted accumulative release of basic cations upon addition of ph..* H,SO. and mixed solutions. ph..* H,SO. SO. Fig. +* Measured and predicted SO. accumulative adsorption after addition of ph..* H, SO. and mixed solutions.. SO. NO - :SO. *.1/ : *.,/ *./* : *./* *.,/ : *.1/ *.** : +.** 2-2- 2. 2/ NO - :SO. *.1/ : *.,/ 0 SO. SO. NO -,SO. NO -,SO. + ph-p Al - HNO -,H,SO., ph Al - HNO - H,SO. + - + NO - Cl SO. + ph NO -,SO. NO - ph. ph Mixing Cell Appelo and Willemsen, +321 NO -,SO. Appelo, C.A. J. and Willemsen, A. (+321) : Geochemical calculations and observation on salt water intrusions, I. A combined geochemical/mixing
: 11 cell model. J. Hydrol., 3. : -+---*. Bloom, P.R. and Grigal, D.F. (+32/) : Modeling soil response to acidic deposition in nonsulfate adsorbing soils. J. Environ. Qual., +. :.23.3/. Bolt, G.H. and Bruggenwert (+32*) : pp. 33 +*/ +331 : pp.,+,+/ Fumoto, T., Shindo, J., Oura, N. and Sverdrup, H. (,**+) : Adapting the profile model to calculate the critical loads for East Asian soils by including volcanic glass weathering and alternative solubility system. Water, Air and Soil pollution, +-* : +,.1+,/,. Helgeson, H.C., Murphy, W.M. and Aagaard, P. (+32.): Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solution.,. Rate constants,e#ective surface area, and the hydrolysis of feldfer. Geochimica et cosmochimica Acta,.2 :,.*/,.-,. Huete, A.R. and Mc Coll, J.G.(+32.) : Soil Cation leaching by Acid Rain with Varying Nitrate-to- Sulfate Ratios. J. Environ. Qual., +- : -00-1+. +32* :, /+ : 3/+*+. James, B. J. and Riha, S.R. (+323) : Aluminum leaching by mineral acids in forest soils : I. Nitric-sulfuric acid di#erences. Soil Sci. Soc. Am. J., /- :,/3,0..,** : 23 :,/--. Kamewada, K. (+330) : Application of Four-plane model to the adsorption of K,NO - and SO. from a mixed solution of KNO - and K, SO. on Andisols. Soil Sci. Plant Nutr.,., : 2*+2*2.,** : +. pp. +*2+*3 +332 : ph. 11 : +++2. Mesquita, M.E. and Vieira e Silva, J.M. (,**,) : Preliminary study of ph e#ect in the application of Langmuir and Freundlich isotherms to Cu-Zn competitive adsorption. Geoderma, +*0 :,+3,-.. +33+ : +33+ : 3,*3,3. +332 : +* : 0.20.3. Sato, K., Wakamatsu, T. and Takahashi, A. (+332) : Acid deposition and ecosystem sensitivity in East Asia. pp. +,/+.,, Bashkin, V.N. and Park, S. U. eds., Nova Science Publishers Inc., New York. +332 : 03 :.11.21. +331 : +* :,21,33. +32+ : pp. //1 +331 : pp. 1-3/ Wolt, J.D. (+33.) : Soil solution chemistry. pp. +/2+0+, John Wiley & Sons Inc., New York. +322 : /3 :.+-.+/. Xu, R.K. and Ji, G.L. (,**+) :E#ects of H,SO. and HNO - on soil acidification and aluminum speciation in variable and constant charge soils. Water, Air and Soil Pollution, +,3 : --.-. :,**, /,+ :,**- +,3