MODULE p4zche !!====================================================================== !! *** MODULE p4zche *** !! TOP : PISCES Sea water chemistry computed following OCMIP protocol !!====================================================================== !! History : - ! 1988 (E. Maier-Reimer) Original code !! - ! 1998 (O. Aumont) addition !! - ! 1999 (C. Le Quere) modification !! 1.0 ! 2004 (O. Aumont) modification !! - ! 2006 (R. Gangsto) modification !! 2.0 ! 2007-12 (C. Ethe, G. Madec) F90 !!---------------------------------------------------------------------- #if defined key_pisces !!---------------------------------------------------------------------- !! 'key_pisces' PISCES bio-model !!---------------------------------------------------------------------- !! p4z_che : Sea water chemistry computed following OCMIP protocol !!---------------------------------------------------------------------- USE oce_trc ! USE trp_trc ! USE sms ! IMPLICIT NONE PRIVATE PUBLIC p4z_che ! called in p4zprg.F90 !!* Substitution #include "domzgr_substitute.h90" !!---------------------------------------------------------------------- !! NEMO/TOP 2.0 , LOCEAN-IPSL (2007) !! $Header:$ !! Software governed by the CeCILL licence (modipsl/doc/NEMO_CeCILL.txt) !!---------------------------------------------------------------------- CONTAINS SUBROUTINE p4z_che !!--------------------------------------------------------------------- !! *** ROUTINE p4z_che *** !! !! ** Purpose : Sea water chemistry computed following OCMIP protocol !! !! ** Method : - ... !!--------------------------------------------------------------------- INTEGER :: ji, jj, jk REAL(wp) :: ztkel, zsal , zqtt , zbuf1 , zbuf2 REAL(wp) :: zpres, ztc , zcl , zcpexp, zcek0, zoxy , zcpexp2 REAL(wp) :: zsqrt, ztr , zlogt , zcek1 REAL(wp) :: zlqtt, zqtt2, zsal15, zis , zis2 , zisqrt REAL(wp) :: zckb , zck1 , zck2 , zckw , zak1 , zak2 , zakb , zaksp0, zakw REAL(wp) :: zckp1, zckp2, zckp3 , zcksi , zakp1, zakp2 , zakp3, zaksi REAL(wp) :: zst , zft , zcks , zckf , zaks , zakf , zaksp1 !!--------------------------------------------------------------------- ! CHEMICAL CONSTANTS - SURFACE LAYER ! ---------------------------------- DO jj = 1, jpj DO ji = 1, jpi ! ! SET ABSOLUTE TEMPERATURE ztkel = tn(ji,jj,1) + 273.16 zqtt = ztkel * 0.01 zqtt2 = zqtt * zqtt zsal = sn(ji,jj,1) + (1.- tmask(ji,jj,1) ) * 35. zlqtt = LOG( zqtt ) ! ! LN(K0) OF SOLUBILITY OF CO2 (EQ. 12, WEISS, 1980) ! ! AND FOR THE ATMOSPHERE FOR NON IDEAL GAS zcek0 = c00 + c01 / zqtt + c02 * zlqtt + zsal * ( c03 + c04 * zqtt + c05 * zqtt2 ) zcek1 = ca0 + ca1 / zqtt + ca2 * zlqtt + ca3 * zqtt2 + zsal*( ca4 + ca5 * zqtt + ca6 * zqtt2 ) ! ! LN(K0) OF SOLUBILITY OF O2 and N2 (EQ. 4, WEISS, 1970) zoxy = ox0 + ox1 / zqtt + ox2 * zlqtt + zsal * ( ox3 + ox4 * zqtt + ox5 * zqtt2 ) ! ! SET SOLUBILITIES OF O2 AND CO2 chemc(ji,jj,1) = EXP( zcek0 ) * 1.e-6 * rhop(ji,jj,1) / 1000. chemc(ji,jj,2) = EXP( zoxy ) * oxyco chemc(ji,jj,3) = EXP( zcek1 ) * 1.e-6 * rhop(ji,jj,1) / 1000. END DO END DO ! CHEMICAL CONSTANTS - DEEP OCEAN ! ------------------------------- DO jk = 1, jpk DO jj = 1, jpj DO ji = 1, jpi ! SET PRESSION zpres = 1.025e-1 * fsdept(ji,jj,jk) ! SET ABSOLUTE TEMPERATURE ztkel = tn(ji,jj,jk) + 273.16 zqtt = ztkel * 0.01 zsal = sn(ji,jj,jk) + ( 1.-tmask(ji,jj,jk) ) * 35. zsqrt = SQRT( zsal ) zsal15 = zsqrt * zsal zlogt = LOG( ztkel ) ztr = 1. / ztkel zis = 19.924 * zsal / ( 1000.- 1.005 * zsal ) zis2 = zis * zis zisqrt = SQRT( zis ) ztc = tn(ji,jj,jk) + ( 1.- tmask(ji,jj,jk) ) * 20. ! CHLORINITY (WOOSTER ET AL., 1969) zcl = zsal * salchl ! TOTAL SULFATE CONCENTR. [MOLES/kg soln] zst = st1 * zcl * st2 ! TOTAL FLUORIDE CONCENTR. [MOLES/kg soln] zft = ft1 * zcl * ft2 ! DISSOCIATION CONSTANT FOR SULFATES on free H scale (Dickson 1990) zcks = EXP( ks1 * ztr + ks0 + ks2 * zlogt & & + ( ks3 * ztr + ks4 + ks5 * zlogt ) * zisqrt & & + ( ks6 * ztr + ks7 + ks8 * zlogt ) * zis & & + ks9 * ztr * zis * zisqrt + ks10 * ztr *zis2 + LOG( ks11 + ks12 *zsal ) ) ! DISSOCIATION CONSTANT FOR FLUORIDES on free H scale (Dickson and Riley 79) zckf = EXP( kf1 * ztr + kf0 + kf2 * zisqrt + LOG( kf3 + kf4 * zsal ) ) ! DISSOCIATION CONSTANT FOR CARBONATE AND BORATE zckb = ( cb0 + cb1 * zsqrt + cb2 * zsal + cb3 * zsal15 + cb4 * zsal * zsal ) * ztr & & + ( cb5 + cb6 * zsqrt + cb7 * zsal ) & & + ( cb8 + cb9 * zsqrt + cb10 * zsal ) * zlogt + cb11 * zsqrt * ztkel & & + LOG( ( 1.+ zst / zcks + zft / zckf ) / ( 1.+ zst / zcks ) ) !!gm zsal**2 to be replaced by a *... zck1 = c10 * ztr + c11 + c12 * zlogt + c13 * zsal + c14 * zsal**2 zck2 = c20 * ztr + c21 + c22 * zsal + c23 * zsal**2 ! PKW (H2O) (DICKSON AND RILEY, 1979) zckw = cw0 * ztr + cw1 + cw2 * zlogt + ( cw3 * ztr + cw4 + cw5 * zlogt ) * zsqrt + cw6 * zsal ! DISSOCIATION CONSTANT FOR PHOSPHATE AND SILICATE (seawater scale) zckp1 = cp10 + cp11 * ztr + cp12 * zlogt + zsqrt * ( cp13 * ztr + cp14 ) + zsal * ( cp15 * ztr + cp16 ) zckp2 = cp20 + cp21 * ztr + cp22 * zlogt + zsqrt * ( cp23 * ztr + cp24 ) + zsal * ( cp25 * ztr + cp26 ) zckp3 = cp30 + cp31 * ztr + zsqrt * ( cp32 * ztr + cp33 ) + zsal * ( cp34 * ztr + cp35 ) zcksi = cs10 + cs11 * ztr + cs12 * zlogt + zisqrt* ( cs13 * ztr + cs14 ) + zis * ( cs15 * ztr + cs16 ) & & + zis2 * ( cs17 * ztr + cs18 ) + LOG( 1. + cs19 * zsal ) & & + LOG( cs20 + cs21 * zsal ) ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE IN SEAWATER ! (S=27-43, T=2-25 DEG C) at pres =0 (atmos. pressure) (MUCCI 1983) zaksp0 = akcc1 + akcc2 * ztkel + akcc3 * ztr + akcc4 * LOG10( ztkel ) & & + ( akcc5 + akcc6 * ztkel + akcc7 * ztr ) * zsqrt + akcc8 * zsal + akcc9 * zsal15 ! K1, K2 OF CARBONIC ACID, KB OF BORIC ACID, KW (H2O) (LIT.?) zak1 = 10**(zck1) zak2 = 10**(zck2) zakb = EXP( zckb ) zakp1 = EXP( zckp1 ) zakp2 = EXP( zckp2 ) zakp3 = EXP( zckp3 ) zaksi = EXP( zcksi ) zakw = EXP( zckw ) zaksp1 = 10**(zaksp0) zaks = exp( zcks ) zakf = exp( zckf ) ! FORMULA FOR CPEXP AFTER EDMOND & GIESKES (1970) ! (REFERENCE TO CULBERSON & PYTKOQICZ (1968) AS MADE ! IN BROECKER ET AL. (1982) IS INCORRECT; HERE RGAS IS ! TAKEN TENFOLD TO CORRECT FOR THE NOTATION OF pres IN ! DBAR INSTEAD OF BAR AND THE EXPRESSION FOR CPEXP IS ! MULTIPLIED BY LN(10.) TO ALLOW USE OF EXP-FUNCTION ! WITH BASIS E IN THE FORMULA FOR AKSPP (CF. EDMOND ! & GIESKES (1970), P. 1285-1286 (THE SMALL ! FORMULA ON P. 1286 IS RIGHT AND CONSISTENT WITH THE ! SIGN IN PARTIAL MOLAR VOLUME CHANGE AS SHOWN ON P. 1285)) zcpexp = zpres /(rgas*ztkel) zcpexp2 = zpres * zpres/(rgas*ztkel) ! KB OF BORIC ACID, K1,K2 OF CARBONIC ACID PRESSURE ! CORRECTION AFTER CULBERSON AND PYTKOWICZ (1968) ! (CF. BROECKER ET AL., 1982) zbuf1 = - ( devk1(3) + devk2(3) * ztc + devk3(3) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(3) + devk5(3) * ztc ) akb3(ji,jj,jk) = zakb * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = -(devk1(1)+devk2(1)*ztc+devk3(1)*ztc*ztc) zbuf2 = 0.5*(devk4(1)+devk5(1)*ztc) ak13(ji,jj,jk) = zak1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk1(2) + devk2(2) * ztc + devk3(2) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(2) + devk5(2) * ztc ) ak23(ji,jj,jk) = zak2 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk1(4) + devk2(4) * ztc + devk3(4) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(4) + devk5(4) * ztc ) akp13(ji,jj,jk) = zakp1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk1(5) + devk2(5) * ztc + devk3(5) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(5) + devk5(5) * ztc ) akp23(ji,jj,jk) = zakp2 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk1(6) + devk2(6) * ztc + devk3(6) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(6) + devk5(6) * ztc ) akp33(ji,jj,jk) = zakp3 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk1(7) + devk2(7) * ztc + devk3(7) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(7) + devk5(7) * ztc ) akw3(ji,jj,jk) = zakw * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) ! Ksi ! aksi3(ji,jj,jk) = zaksi ! ! Or using coefficient of borates (cf millero 95+ corrected version html doc co2sys) ! "deltaVsi and deltaKsi have been estimated from the value of boric acid" zbuf1 = - ( devk1(3) + devk2(3) * ztc + devk3(3) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(3) + devk5(3) * ztc ) aksi3(ji,jj,jk) = zaksi * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE ! AS FUNCTION OF PRESSURE FOLLOWING MILLERO ! (P. 1285) AND BERNER (1976) zbuf1 = - ( devk1(8) + devk2(8) * ztc + devk3(8) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(8) + devk5(8) * ztc ) aksp(ji,jj,jk) = zaksp1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) ! Pressure correction for sulfate and fluoride zbuf1 = - ( devk1(9) + devk2(9) * ztc + devk3(9) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(9) + devk5(9) * ztc ) aks3(ji,jj,jk) = zaks * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk1(10) + devk2(10) * ztc + devk3(10) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(10) + devk5(10) * ztc ) akf3(ji,jj,jk) = zakf * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) ! TOTAL BORATE CONCENTR. [MOLES/L] borat(ji,jj,jk) = bor1 * zcl * bor2 ! Iron and SIO3 saturation concentration from ... sio3eq(ji,jj,jk) = EXP( LOG( 10.) * ( 6.44 - 968. / ztkel ) ) * 1.e-6 fekeq (ji,jj,jk) = 10**( 17.27 - 1565.7 / ( 273.15 + ztc ) ) END DO END DO END DO ! END SUBROUTINE p4z_che #else !!====================================================================== !! Dummy module : No PISCES bio-model !!====================================================================== CONTAINS SUBROUTINE p4z_che( kt ) ! Empty routine INTEGER, INTENT( in ) :: kt WRITE(*,*) 'p4z_che: You should not have seen this print! error?', kt END SUBROUTINE p4z_che #endif !!====================================================================== END MODULE p4zche