MODULE p4zche !!====================================================================== !! *** MODULE p4zche *** !! TOP : PISCES Sea water chemistry computed following OCMIP protocol !!====================================================================== !! History : OPA ! 1988 (E. Maier-Reimer) Original code !! - ! 1998 (O. Aumont) addition !! - ! 1999 (C. Le Quere) modification !! NEMO 1.0 ! 2004 (O. Aumont) modification !! - ! 2006 (R. Gangsto) modification !! 2.0 ! 2007-12 (C. Ethe, G. Madec) F90 !! ! 2011-02 (J. Simeon, J.Orr ) update O2 solubility constants !!---------------------------------------------------------------------- #if defined key_pisces !!---------------------------------------------------------------------- !! 'key_pisces' PISCES bio-model !!---------------------------------------------------------------------- !! p4z_che : Sea water chemistry computed following OCMIP protocol !!---------------------------------------------------------------------- USE oce_trc ! shared variables between ocean and passive tracers USE trc ! passive tracers common variables USE sms_pisces ! PISCES Source Minus Sink variables USE lib_mpp ! MPP library IMPLICIT NONE PRIVATE PUBLIC p4z_che ! PUBLIC p4z_che_alloc ! REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: sio3eq ! chemistry of Si REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: fekeq ! chemistry of Fe REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: chemc ! Solubilities of O2 and CO2 REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: chemo2 ! Solubilities of O2 and CO2 REAL(wp), PUBLIC :: atcox = 0.20946 ! units atm REAL(wp) :: salchl = 1. / 1.80655 ! conversion factor for salinity --> chlorinity (Wooster et al. 1969) REAL(wp) :: o2atm = 1. / ( 1000. * 0.20946 ) REAL(wp) :: akcc1 = -171.9065 ! coeff. for apparent solubility equilibrium REAL(wp) :: akcc2 = -0.077993 ! Millero et al. 1995 from Mucci 1983 REAL(wp) :: akcc3 = 2839.319 REAL(wp) :: akcc4 = 71.595 REAL(wp) :: akcc5 = -0.77712 REAL(wp) :: akcc6 = 0.00284263 REAL(wp) :: akcc7 = 178.34 REAL(wp) :: akcc8 = -0.07711 REAL(wp) :: akcc9 = 0.0041249 REAL(wp) :: rgas = 83.143 ! universal gas constants REAL(wp) :: oxyco = 1. / 22.4144 ! converts from liters of an ideal gas to moles REAL(wp) :: bor1 = 0.00023 ! borat constants REAL(wp) :: bor2 = 1. / 10.82 REAL(wp) :: ca0 = -162.8301 ! WEISS & PRICE 1980, units mol/(kg atm) REAL(wp) :: ca1 = 218.2968 REAL(wp) :: ca2 = 90.9241 REAL(wp) :: ca3 = -1.47696 REAL(wp) :: ca4 = 0.025695 REAL(wp) :: ca5 = -0.025225 REAL(wp) :: ca6 = 0.0049867 REAL(wp) :: c10 = -3670.7 ! Coeff. for 1. dissoc. of carbonic acid (Edmond and Gieskes, 1970) REAL(wp) :: c11 = 62.008 REAL(wp) :: c12 = -9.7944 REAL(wp) :: c13 = 0.0118 REAL(wp) :: c14 = -0.000116 REAL(wp) :: c20 = -1394.7 ! coeff. for 2. dissoc. of carbonic acid (Millero, 1995) REAL(wp) :: c21 = -4.777 REAL(wp) :: c22 = 0.0184 REAL(wp) :: c23 = -0.000118 REAL(wp) :: st1 = 0.14 ! constants for calculate concentrations for sulfate REAL(wp) :: st2 = 1./96.062 ! (Morris & Riley 1966) REAL(wp) :: ks0 = 141.328 REAL(wp) :: ks1 = -4276.1 REAL(wp) :: ks2 = -23.093 REAL(wp) :: ks3 = -13856. REAL(wp) :: ks4 = 324.57 REAL(wp) :: ks5 = -47.986 REAL(wp) :: ks6 = 35474. REAL(wp) :: ks7 = -771.54 REAL(wp) :: ks8 = 114.723 REAL(wp) :: ks9 = -2698. REAL(wp) :: ks10 = 1776. REAL(wp) :: ks11 = 1. REAL(wp) :: ks12 = -0.001005 REAL(wp) :: ft1 = 0.000067 ! constants for calculate concentrations for fluorides REAL(wp) :: ft2 = 1./18.9984 ! (Dickson & Riley 1979 ) REAL(wp) :: kf0 = -12.641 REAL(wp) :: kf1 = 1590.2 REAL(wp) :: kf2 = 1.525 REAL(wp) :: kf3 = 1.0 REAL(wp) :: kf4 = -0.001005 REAL(wp) :: cb0 = -8966.90 ! Coeff. for 1. dissoc. of boric acid REAL(wp) :: cb1 = -2890.53 ! (Dickson and Goyet, 1994) REAL(wp) :: cb2 = -77.942 REAL(wp) :: cb3 = 1.728 REAL(wp) :: cb4 = -0.0996 REAL(wp) :: cb5 = 148.0248 REAL(wp) :: cb6 = 137.1942 REAL(wp) :: cb7 = 1.62142 REAL(wp) :: cb8 = -24.4344 REAL(wp) :: cb9 = -25.085 REAL(wp) :: cb10 = -0.2474 REAL(wp) :: cb11 = 0.053105 REAL(wp) :: cw0 = -13847.26 ! Coeff. for dissoc. of water (Dickson and Riley, 1979 ) REAL(wp) :: cw1 = 148.9652 REAL(wp) :: cw2 = -23.6521 REAL(wp) :: cw3 = 118.67 REAL(wp) :: cw4 = -5.977 REAL(wp) :: cw5 = 1.0495 REAL(wp) :: cw6 = -0.01615 ! ! volumetric solubility constants for o2 in ml/L REAL(wp) :: ox0 = 2.00856 ! from Table 1 for Eq 8 of Garcia and Gordon, 1992. REAL(wp) :: ox1 = 3.22400 ! corrects for moisture and fugacity, but not total atmospheric pressure REAL(wp) :: ox2 = 3.99063 ! Original PISCES code noted this was a solubility, but REAL(wp) :: ox3 = 4.80299 ! was in fact a bunsen coefficient with units L-O2/(Lsw atm-O2) REAL(wp) :: ox4 = 9.78188e-1 ! Hence, need to divide EXP( zoxy ) by 1000, ml-O2 => L-O2 REAL(wp) :: ox5 = 1.71069 ! and atcox = 0.20946 to add the 1/atm dimension. REAL(wp) :: ox6 = -6.24097e-3 REAL(wp) :: ox7 = -6.93498e-3 REAL(wp) :: ox8 = -6.90358e-3 REAL(wp) :: ox9 = -4.29155e-3 REAL(wp) :: ox10 = -3.11680e-7 ! ! coeff. for seawater pressure correction : millero 95 ! ! AGRIF doesn't like the DATA instruction REAL(wp) :: devk11 = -25.5 REAL(wp) :: devk12 = -15.82 REAL(wp) :: devk13 = -29.48 REAL(wp) :: devk14 = -25.60 REAL(wp) :: devk15 = -48.76 ! REAL(wp) :: devk21 = 0.1271 REAL(wp) :: devk22 = -0.0219 REAL(wp) :: devk23 = 0.1622 REAL(wp) :: devk24 = 0.2324 REAL(wp) :: devk25 = 0.5304 ! REAL(wp) :: devk31 = 0. REAL(wp) :: devk32 = 0. REAL(wp) :: devk33 = 2.608E-3 REAL(wp) :: devk34 = -3.6246E-3 REAL(wp) :: devk35 = 0. ! REAL(wp) :: devk41 = -3.08E-3 REAL(wp) :: devk42 = 1.13E-3 REAL(wp) :: devk43 = -2.84E-3 REAL(wp) :: devk44 = -5.13E-3 REAL(wp) :: devk45 = -11.76E-3 ! REAL(wp) :: devk51 = 0.0877E-3 REAL(wp) :: devk52 = -0.1475E-3 REAL(wp) :: devk53 = 0. REAL(wp) :: devk54 = 0.0794E-3 REAL(wp) :: devk55 = 0.3692E-3 !!* Substitution #include "top_substitute.h90" !!---------------------------------------------------------------------- !! NEMO/TOP 3.3 , NEMO Consortium (2010) !! $Id$ !! Software governed by the CeCILL licence (NEMOGCM/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, zt , zt2 , zsal , zsal2 , zbuf1 , zbuf2 REAL(wp) :: ztgg , ztgg2, ztgg3 , ztgg4 , ztgg5 REAL(wp) :: zpres, ztc , zcl , zcpexp, zoxy , zcpexp2 REAL(wp) :: zsqrt, ztr , zlogt , zcek1 REAL(wp) :: zis , zis2 , zsal15, zisqrt REAL(wp) :: zckb , zck1 , zck2 , zckw , zak1 , zak2 , zakb , zaksp0, zakw REAL(wp) :: zst , zft , zcks , zckf , zaksp1 !!--------------------------------------------------------------------- ! IF( nn_timing == 1 ) CALL timing_start('p4z_che') ! ! CHEMICAL CONSTANTS - SURFACE LAYER ! ---------------------------------- !CDIR NOVERRCHK DO jj = 1, jpj !CDIR NOVERRCHK DO ji = 1, jpi ! ! SET ABSOLUTE TEMPERATURE ztkel = tsn(ji,jj,1,jp_tem) + 273.16 zt = ztkel * 0.01 zt2 = zt * zt zsal = tsn(ji,jj,1,jp_sal) + ( 1.- tmask(ji,jj,1) ) * 35. zsal2 = zsal * zsal zlogt = LOG( zt ) ! ! LN(K0) OF SOLUBILITY OF CO2 (EQ. 12, WEISS, 1980) ! ! AND FOR THE ATMOSPHERE FOR NON IDEAL GAS zcek1 = ca0 + ca1 / zt + ca2 * zlogt + ca3 * zt2 + zsal * ( ca4 + ca5 * zt + ca6 * zt2 ) ! ! LN(K0) OF SOLUBILITY OF O2 and N2 in ml/L (EQ. 8, GARCIA AND GORDON, 1992) ztgg = LOG( ( 298.15 - tsn(ji,jj,1,jp_tem) ) / ztkel ) ! Set the GORDON & GARCIA scaled temperature ztgg2 = ztgg * ztgg ztgg3 = ztgg2 * ztgg ztgg4 = ztgg3 * ztgg ztgg5 = ztgg4 * ztgg zoxy = ox0 + ox1 * ztgg + ox2 * ztgg2 + ox3 * ztgg3 + ox4 * ztgg4 + ox5 * ztgg5 & + zsal * ( ox6 + ox7 * ztgg + ox8 * ztgg2 + ox9 * ztgg3 ) + ox10 * zsal2 ! ! SET SOLUBILITIES OF O2 AND CO2 chemc(ji,jj,1) = EXP( zcek1 ) * 1.e-6 * rhop(ji,jj,1) / 1000. ! mol/(L uatm) chemc(ji,jj,2) = ( EXP( zoxy ) * o2atm ) * oxyco ! mol/(L atm) ! END DO END DO ! OXYGEN SOLUBILITY - DEEP OCEAN ! ------------------------------- !CDIR NOVERRCHK DO jk = 1, jpk !CDIR NOVERRCHK DO jj = 1, jpj !CDIR NOVERRCHK DO ji = 1, jpi ztkel = tsn(ji,jj,jk,jp_tem) + 273.16 zsal = tsn(ji,jj,jk,jp_sal) + ( 1.- tmask(ji,jj,jk) ) * 35. zsal2 = zsal * zsal ztgg = LOG( ( 298.15 - tsn(ji,jj,jk,jp_tem) ) / ztkel ) ! Set the GORDON & GARCIA scaled temperature ztgg2 = ztgg * ztgg ztgg3 = ztgg2 * ztgg ztgg4 = ztgg3 * ztgg ztgg5 = ztgg4 * ztgg zoxy = ox0 + ox1 * ztgg + ox2 * ztgg2 + ox3 * ztgg3 + ox4 * ztgg4 + ox5 * ztgg5 & + zsal * ( ox6 + ox7 * ztgg + ox8 * ztgg2 + ox9 * ztgg3 ) + ox10 * zsal2 chemo2(ji,jj,jk) = ( EXP( zoxy ) * o2atm ) * oxyco * atcox ! mol/(L atm) END DO END DO END DO ! CHEMICAL CONSTANTS - DEEP OCEAN ! ------------------------------- !CDIR NOVERRCHK DO jk = 1, jpk !CDIR NOVERRCHK DO jj = 1, jpj !CDIR NOVERRCHK DO ji = 1, jpi ! SET PRESSION zpres = 1.025e-1 * fsdept(ji,jj,jk) ! SET ABSOLUTE TEMPERATURE ztkel = tsn(ji,jj,jk,jp_tem) + 273.16 zsal = tsn(ji,jj,jk,jp_sal) + ( 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 = tsn(ji,jj,jk,jp_tem) + ( 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 ) ) zck1 = c10 * ztr + c11 + c12 * zlogt + c13 * zsal + c14 * zsal * zsal 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 ! 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 ) zakw = EXP( zckw ) zaksp1 = 10**(zaksp0) ! 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 = - ( devk11 + devk21 * ztc + devk31 * ztc * ztc ) zbuf2 = 0.5 * ( devk41 + devk51 * ztc ) ak13(ji,jj,jk) = zak1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk12 + devk22 * ztc + devk32 * ztc * ztc ) zbuf2 = 0.5 * ( devk42 + devk52 * ztc ) ak23(ji,jj,jk) = zak2 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk13 + devk23 * ztc + devk33 * ztc * ztc ) zbuf2 = 0.5 * ( devk43 + devk53 * ztc ) akb3(ji,jj,jk) = zakb * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) zbuf1 = - ( devk14 + devk24 * ztc + devk34 * ztc * ztc ) zbuf2 = 0.5 * ( devk44 + devk54 * ztc ) akw3(ji,jj,jk) = zakw * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE ! AS FUNCTION OF PRESSURE FOLLOWING MILLERO ! (P. 1285) AND BERNER (1976) zbuf1 = - ( devk15 + devk25 * ztc + devk35 * ztc * ztc ) zbuf2 = 0.5 * ( devk45 + devk55 * ztc ) aksp(ji,jj,jk) = zaksp1 * 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 ! IF( nn_timing == 1 ) CALL timing_stop('p4z_che') ! END SUBROUTINE p4z_che INTEGER FUNCTION p4z_che_alloc() !!---------------------------------------------------------------------- !! *** ROUTINE p4z_che_alloc *** !!---------------------------------------------------------------------- ALLOCATE( sio3eq(jpi,jpj,jpk), fekeq(jpi,jpj,jpk), chemc(jpi,jpj,2), chemo2(jpi,jpj,jpk), STAT=p4z_che_alloc ) ! IF( p4z_che_alloc /= 0 ) CALL ctl_warn('p4z_che_alloc : failed to allocate arrays.') ! END FUNCTION p4z_che_alloc #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