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, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: tempis ! In situ temperature 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) :: rgas = 83.14472 ! 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) :: st1 = 0.14 ! constants for calculate concentrations for sulfate REAL(wp) :: st2 = 1./96.062 ! (Morris & Riley 1966) REAL(wp) :: ft1 = 0.000067 ! constants for calculate concentrations for fluorides REAL(wp) :: ft2 = 1./18.9984 ! (Dickson & Riley 1979 ) ! ! 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, zc1, zplat REAL(wp) :: zis , zis2 , zsal15, zisqrt, za1 , za2 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') ! ! Computations of chemical constants require in situ temperature ! Here a quite simple formulation is used to convert ! potential temperature to in situ temperature. The errors is less than ! 0.04°C relative to an exact computation ! --------------------------------------------------------------------- DO jk = 1, jpk DO jj = 1, jpj DO ji = 1, jpi zpres = fsdept(ji,jj,jk) / 1000. za1 = 0.04 * ( 1.0 + 0.185 * tsn(ji,jj,jk,jp_tem) + 0.035 * (tsn(ji,jj,jk,jp_sal) - 35.0) ) za2 = 0.0075 * ( 1.0 - tsn(ji,jj,jk,jp_tem) / 30.0 ) tempis(ji,jj,jk) = tsn(ji,jj,jk,jp_tem) - za1 * zpres + za2 * zpres**2 END DO END DO END DO ! ! CHEMICAL CONSTANTS - SURFACE LAYER ! ---------------------------------- !CDIR NOVERRCHK DO jj = 1, jpj !CDIR NOVERRCHK DO ji = 1, jpi ! ! SET ABSOLUTE TEMPERATURE ztkel = tempis(ji,jj,1) + 273.15 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 = 9345.17/ztkel - 60.2409 + 23.3585 * LOG(zt) + zsal*(0.023517 - 0.00023656*ztkel & & + 0.0047036e-4*ztkel**2) ! ! SET SOLUBILITIES OF O2 AND CO2 chemc(ji,jj,1) = EXP( zcek1 ) * 1.e-6 * rhop(ji,jj,1) / 1000. ! mol/(kg uatm) chemc(ji,jj,2) = -1636.75 + 12.0408*ztkel - 0.0327957*ztkel**2 + 0.0000316528*ztkel**3 chemc(ji,jj,3) = 57.7 - 0.118*ztkel ! 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 = tempis(ji,jj,jk) + 273.15 zsal = tsn(ji,jj,jk,jp_sal) + ( 1.- tmask(ji,jj,jk) ) * 35. zsal2 = zsal * zsal ztgg = LOG( ( 298.15 - tempis(ji,jj,jk) ) / 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 ACCORDING TO SAUNDER (1980) zplat = SIN ( ABS(gphit(ji,jj)*3.141592654/180.) ) zc1 = 5.92E-3 + zplat**2 * 5.25E-3 zpres = ((1-zc1)-SQRT(((1-zc1)**2)-(8.84E-6*fsdept(ji,jj,jk)))) / 4.42E-6 zpres = zpres / 10.0 ! SET ABSOLUTE TEMPERATURE ztkel = tempis(ji,jj,jk) + 273.15 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 = tempis(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(-4276.1 * ztr + 141.328 - 23.093 * zlogt & & + (-13856. * ztr + 324.57 - 47.986 * zlogt) * zisqrt & & + (35474. * ztr - 771.54 + 114.723 * zlogt) * zis & & - 2698. * ztr * zis**1.5 + 1776.* ztr * zis2 & & + LOG(1.0 - 0.001005 * zsal)) ! aphscale(ji,jj,jk) = ( 1. + zst / zcks ) ! DISSOCIATION CONSTANT FOR FLUORIDES on free H scale (Dickson and Riley 79) zckf = EXP( 1590.2*ztr - 12.641 + 1.525*zisqrt & & + LOG(1.0d0 - 0.001005d0*zsal) & & + LOG(1.0d0 + zst/zcks)) ! DISSOCIATION CONSTANT FOR CARBONATE AND BORATE zckb= (-8966.90 - 2890.53*zsqrt - 77.942*zsal & & + 1.728*zsal15 - 0.0996*zsal*zsal)*ztr & & + (148.0248 + 137.1942*zsqrt + 1.62142*zsal) & & + (-24.4344 - 25.085*zsqrt - 0.2474*zsal) & & * zlogt + 0.053105*zsqrt*ztkel ! DISSOCIATION COEFFICIENT FOR CARBONATE ACCORDING TO ! MEHRBACH (1973) REFIT BY MILLERO (1995), seawater scale zck1 = -1.0*(3633.86*ztr - 61.2172 + 9.6777*zlogt & - 0.011555*zsal + 0.0001152*zsal*zsal) zck2 = -1.0*(471.78*ztr + 25.9290 - 3.16967*zlogt & - 0.01781*zsal + 0.0001122*zsal*zsal) ! PKW (H2O) (DICKSON AND RILEY, 1979) zckw = -13847.26*ztr + 148.9652 - 23.6521 * zlogt & & + (118.67*ztr - 5.977 + 1.0495 * zlogt) & & * zsqrt - 0.01615 * 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 = -171.9065 -0.077993*ztkel + 2839.319*ztr + 71.595*LOG10( ztkel ) & & + (-0.77712 + 0.00284263*ztkel + 178.34*ztr) * zsqrt & & - 0.07711*zsal + 0.0041249*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,3), chemo2(jpi,jpj,jpk), & & tempis(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