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 trc ! USE sms_pisces ! IMPLICIT NONE PRIVATE PUBLIC p4z_che !! * Shared module variables REAL(wp), PUBLIC, DIMENSION(jpi,jpj,jpk) :: & !: sio3eq, fekeq !: chemistry of Fe and Si REAL(wp), PUBLIC, DIMENSION(jpi,jpj,2) :: & !: chemc !: Solubilities of O2 and CO2 !! * Module variables REAL(wp) :: & salchl = 1./1.80655 ! conversion factor for salinity --> chlorinity (Wooster et al. 1969) REAL(wp) :: & ! coeff. for apparent solubility equilibrium akcc1 = -171.9065 , & ! Millero et al. 1995 from Mucci 1983 akcc2 = -0.077993 , & akcc3 = 2839.319 , & akcc4 = 71.595 , & akcc5 = -0.77712 , & akcc6 = 0.0028426 , & akcc7 = 178.34 , & akcc8 = -0.07711 , & akcc9 = 0.0041249 REAL(wp) :: & ! universal gas constants rgas = 83.143, & oxyco = 1./22.4144 REAL(wp) :: & ! borat constants bor1 = 0.00023, & bor2 = 1./10.82 REAL(wp) :: & ! ca0 = -162.8301 , & ca1 = 218.2968 , & ca2 = 90.9241 , & ca3 = -1.47696 , & ca4 = 0.025695 , & ca5 = -0.025225 , & ca6 = 0.0049867 REAL(wp) :: & ! coeff. for 1. dissoc. of carbonic acid (Edmond and Gieskes, 1970) c10 = -3670.7 , & c11 = 62.008 , & c12 = -9.7944 , & c13 = 0.0118 , & c14 = -0.000116 REAL(wp) :: & ! coeff. for 2. dissoc. of carbonic acid (Millero, 1995) c20 = -1394.7 , & c21 = -4.777 , & c22 = 0.0184 , & c23 = -0.000118 REAL(wp) :: & ! constants for calculate concentrations st1 = 0.14 , & ! for sulfate (Morris & Riley 1966) st2 = 1./96.062, & ks0 = 141.328 , & ks1 = -4276.1 , & ks2 = -23.093 , & ks3 = -13856. , & ks4 = 324.57 , & ks5 = -47.986 , & ks6 = 35474. , & ks7 = -771.54 , & ks8 = 114.723 , & ks9 = -2698. , & ks10 = 1776. , & ks11 = 1. , & ks12 = -0.001005 REAL(wp) :: & ! constants for calculate concentrations ft1 = 0.000067 , & ! fluorides (Dickson & Riley 1979 ) ft2 = 1./18.9984 , & kf0 = -12.641 , & kf1 = 1590.2 , & kf2 = 1.525 , & kf3 = 1.0 , & kf4 =-0.001005 REAL(wp) :: & ! coeff. for 1. dissoc. of boric acid (Dickson and Goyet, 1994) cb0 = -8966.90, & cb1 = -2890.53, & cb2 = -77.942 , & cb3 = 1.728 , & cb4 = -0.0996 , & cb5 = 148.0248, & cb6 = 137.1942, & cb7 = 1.62142 , & cb8 = -24.4344, & cb9 = -25.085 , & cb10 = -0.2474 , & cb11 = 0.053105 REAL(wp) :: & ! coeff. for dissoc. of water (Dickson and Riley, 1979 ) cw0 = -13847.26 , & cw1 = 148.9652 , & cw2 = -23.6521 , & cw3 = 118.67 , & cw4 = -5.977 , & cw5 = 1.0495 , & cw6 = -0.01615 REAL(wp) :: & ! volumetric solubility constants for o2 in ml/l (Weiss, 1974) ox0 = -58.3877 , & ox1 = 85.8079 , & ox2 = 23.8439 , & ox3 = -0.034892 , & ox4 = 0.015568 , & ox5 = -0.0019387 REAL(wp), DIMENSION(5) :: & ! coeff. for seawater pressure correction devk1, devk2, devk3, & ! (millero 95) devk4, devk5 DATA devk1 / -25.5 , -15.82 , -29.48 , -25.60 , -48.76 / DATA devk2 / 0.1271 , -0.0219 , 0.1622 , 0.2324 , 0.5304 / DATA devk3 / 0. , 0. , 2.608E-3, -3.6246E-3, 0. / DATA devk4 / -3.08E-3 , 1.13E-3 , -2.84E-3, -5.13E-3 , -11.76E-3 / DATA devk5 / 0.0877E-3, -0.1475E-3, 0. , 0.0794E-3 , 0.3692E-3 / !!* Substitution #include "top_substitute.h90" !!---------------------------------------------------------------------- !! NEMO/TOP 2.0 , LOCEAN-IPSL (2007) !! $Id$ !! 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, 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) :: zst , zft , zcks , zckf , zaksp1 !!--------------------------------------------------------------------- ! CHEMICAL CONSTANTS - SURFACE LAYER ! ---------------------------------- !CDIR NOVERRCHK DO jj = 1, jpj !CDIR NOVERRCHK 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 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( zcek1 ) * 1.e-6 * rhop(ji,jj,1) / 1000. chemc(ji,jj,2) = EXP( zoxy ) * oxyco 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 = 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 ! 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 = -(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(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(4) + devk2(4) * ztc + devk3(4) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(4) + devk5(4) * 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 = - ( devk1(5) + devk2(5) * ztc + devk3(5) * ztc * ztc ) zbuf2 = 0.5 * ( devk4(5) + devk5(5) * 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 ! 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