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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
!! 3.6 ! 2016-03 (O. Aumont) Change chemistry to MOCSY standards
!!----------------------------------------------------------------------
!! 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
USE eosbn2, ONLY : neos
IMPLICIT NONE
PRIVATE
PUBLIC p4z_che !
PUBLIC p4z_che_alloc !
PUBLIC ahini_for_at !
PUBLIC solve_at_general !
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(:,:,:,:) :: fesol ! solubility of Fe
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: salinprac ! Practical salinity
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: tempis ! In situ temperature
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: akb3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: akw3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: akf3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: aks3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: ak1p3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: ak2p3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: ak3p3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: aksi3 !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: borat !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: fluorid !: ???
REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: sulfat !: ???
!!* Variable for chemistry of the CO2 cycle
REAL(wp), PUBLIC :: atcox = 0.20946 ! units atm
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
! ! coeff. for seawater pressure correction : millero 95
! ! AGRIF doesn't like the DATA instruction
REAL(wp) :: devk10 = -25.5
REAL(wp) :: devk11 = -15.82
REAL(wp) :: devk12 = -29.48
REAL(wp) :: devk13 = -20.02
REAL(wp) :: devk14 = -18.03
REAL(wp) :: devk15 = -9.78
REAL(wp) :: devk16 = -48.76
REAL(wp) :: devk17 = -14.51
REAL(wp) :: devk18 = -23.12
REAL(wp) :: devk19 = -26.57
REAL(wp) :: devk110 = -29.48
!
REAL(wp) :: devk20 = 0.1271
REAL(wp) :: devk21 = -0.0219
REAL(wp) :: devk22 = 0.1622
REAL(wp) :: devk23 = 0.1119
REAL(wp) :: devk24 = 0.0466
REAL(wp) :: devk25 = -0.0090
REAL(wp) :: devk26 = 0.5304
REAL(wp) :: devk27 = 0.1211
REAL(wp) :: devk28 = 0.1758
REAL(wp) :: devk29 = 0.2020
REAL(wp) :: devk210 = 0.1622
!
REAL(wp) :: devk30 = 0.
REAL(wp) :: devk31 = 0.
REAL(wp) :: devk32 = 2.608E-3
REAL(wp) :: devk33 = -1.409e-3
REAL(wp) :: devk34 = 0.316e-3
REAL(wp) :: devk35 = -0.942e-3
REAL(wp) :: devk36 = 0.
REAL(wp) :: devk37 = -0.321e-3
REAL(wp) :: devk38 = -2.647e-3
REAL(wp) :: devk39 = -3.042e-3
REAL(wp) :: devk310 = -2.6080e-3
!
REAL(wp) :: devk40 = -3.08E-3
REAL(wp) :: devk41 = 1.13E-3
REAL(wp) :: devk42 = -2.84E-3
REAL(wp) :: devk43 = -5.13E-3
REAL(wp) :: devk44 = -4.53e-3
REAL(wp) :: devk45 = -3.91e-3
REAL(wp) :: devk46 = -11.76e-3
REAL(wp) :: devk47 = -2.67e-3
REAL(wp) :: devk48 = -5.15e-3
REAL(wp) :: devk49 = -4.08e-3
REAL(wp) :: devk410 = -2.84e-3
!
REAL(wp) :: devk50 = 0.0877E-3
REAL(wp) :: devk51 = -0.1475E-3
REAL(wp) :: devk52 = 0.
REAL(wp) :: devk53 = 0.0794E-3
REAL(wp) :: devk54 = 0.09e-3
REAL(wp) :: devk55 = 0.054e-3
REAL(wp) :: devk56 = 0.3692E-3
REAL(wp) :: devk57 = 0.0427e-3
REAL(wp) :: devk58 = 0.09e-3
REAL(wp) :: devk59 = 0.0714e-3
REAL(wp) :: devk510 = 0.0
!
! General parameters
REAL(wp), PARAMETER :: pp_rdel_ah_target = 1.E-4_wp
REAL(wp), PARAMETER :: pp_ln10 = 2.302585092994045684018_wp
! Maximum number of iterations for each method
INTEGER, PARAMETER :: jp_maxniter_atgen = 20
! Bookkeeping variables for each method
! - SOLVE_AT_GENERAL
INTEGER :: niter_atgen = jp_maxniter_atgen
!! * Substitutions
# include "do_loop_substitute.h90"
# include "domzgr_substitute.h90"
!!----------------------------------------------------------------------
!! NEMO/TOP 4.0 , NEMO Consortium (2018)
!! $Id: p4zche.F90 15459 2021-10-29 08:19:18Z cetlod $
!! Software governed by the CeCILL license (see ./LICENSE)
!!----------------------------------------------------------------------
CONTAINS
SUBROUTINE p4z_che( Kbb, Kmm )
!!---------------------------------------------------------------------
!! *** ROUTINE p4z_che ***
!!
!! ** Purpose : Sea water chemistry computed following OCMIP protocol
!!
!! ** Method : - ...
!!---------------------------------------------------------------------
INTEGER, INTENT(in) :: Kbb, Kmm ! time level indices
INTEGER :: ji, jj, jk
REAL(wp) :: ztkel, ztkel1, zt , 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) :: zck1p, zck2p, zck3p, zcksi, zak1p, zak2p, zak3p, zaksi
REAL(wp) :: zst , zft , zcks , zckf , zaksp1
REAL(wp) :: total2free, free2SWS, total2SWS, SWS2total
!!---------------------------------------------------------------------
!
IF( ln_timing ) CALL timing_start('p4z_che')
!
! Computation of chemical constants require practical salinity
! Thus, when TEOS08 is used, absolute salinity is converted to
! practical salinity
! -------------------------------------------------------------
IF (neos == -1) THEN
salinprac(:,:,:) = ts(:,:,:,jp_sal,Kmm) * 35.0 / 35.16504
ELSE
salinprac(:,:,:) = ts(:,:,:,jp_sal,Kmm)
ENDIF
!
! 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_3D( nn_hls, nn_hls, nn_hls, nn_hls, 1, jpk )
zpres = gdept(ji,jj,jk,Kmm) / 1000.
za1 = 0.04 * ( 1.0 + 0.185 * ts(ji,jj,jk,jp_tem,Kmm) + 0.035 * (salinprac(ji,jj,jk) - 35.0) )
za2 = 0.0075 * ( 1.0 - ts(ji,jj,jk,jp_tem,Kmm) / 30.0 )
tempis(ji,jj,jk) = ts(ji,jj,jk,jp_tem,Kmm) - za1 * zpres + za2 * zpres**2
END_3D
!
! CHEMICAL CONSTANTS - SURFACE LAYER
! ----------------------------------
DO_2D( nn_hls, nn_hls, nn_hls, nn_hls )
! ! SET ABSOLUTE TEMPERATURE
ztkel = tempis(ji,jj,1) + 273.15
zt = ztkel * 0.01
zsal = salinprac(ji,jj,1) + ( 1.- tmask(ji,jj,1) ) * 35.
! ! LN(K0) OF SOLUBILITY OF CO2 (EQ. 12, WEISS, 1980)
! ! AND FOR THE ATMOSPHERE FOR NON IDEAL GAS
zcek1 = 9050.69/ztkel - 58.0931 + 22.2940 * LOG(zt) + zsal*(0.027766 - 0.00025888*ztkel &
& + 0.0050578e-4*ztkel**2)
chemc(ji,jj,1) = EXP( zcek1 ) * 1E-6 ! mol/(L atm)
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_2D
! OXYGEN SOLUBILITY - DEEP OCEAN
! -------------------------------
DO_3D( nn_hls, nn_hls, nn_hls, nn_hls, 1, jpk )
ztkel = tempis(ji,jj,jk) + 273.15
zsal = salinprac(ji,jj,jk) + ( 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 = 2.00856 + 3.22400 * ztgg + 3.99063 * ztgg2 + 4.80299 * ztgg3 &
& + 9.78188e-1 * ztgg4 + 1.71069 * ztgg5 + zsal * ( -6.24097e-3 &
& - 6.93498e-3 * ztgg - 6.90358e-3 * ztgg2 - 4.29155e-3 * ztgg3 ) &
& - 3.11680e-7 * zsal2
chemo2(ji,jj,jk) = ( EXP( zoxy ) * o2atm ) * oxyco * atcox ! mol/(L atm)
END_3D
! CHEMICAL CONSTANTS - DEEP OCEAN
! -------------------------------
DO_3D( nn_hls, nn_hls, nn_hls, nn_hls, 1, jpk )
! 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*gdept(ji,jj,jk,Kmm)))) / 4.42E-6
zpres = zpres / 10.0
! SET ABSOLUTE TEMPERATURE
ztkel = tempis(ji,jj,jk) + 273.15
zsal = salinprac(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 = tempis(ji,jj,jk) + ( 1.- tmask(ji,jj,jk) ) * 20.
! CHLORINITY (WOOSTER ET AL., 1969)
zcl = zsal / 1.80655
! TOTAL SULFATE CONCENTR. [MOLES/kg soln]
zst = 0.14 * zcl /96.062
! TOTAL FLUORIDE CONCENTR. [MOLES/kg soln]
zft = 0.000067 * zcl /18.9984
! 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))
! 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) (MILLERO, 1995) from composite data
zckw = -13847.26 * ztr + 148.9652 - 23.6521 * zlogt + ( 118.67 * ztr &
- 5.977 + 1.0495 * zlogt ) * zsqrt - 0.01615 * zsal
! CONSTANTS FOR PHOSPHATE (MILLERO, 1995)
zck1p = -4576.752*ztr + 115.540 - 18.453*zlogt &
& + (-106.736*ztr + 0.69171) * zsqrt &
& + (-0.65643*ztr - 0.01844) * zsal
zck2p = -8814.715*ztr + 172.1033 - 27.927*zlogt &
& + (-160.340*ztr + 1.3566)*zsqrt &
& + (0.37335*ztr - 0.05778)*zsal
zck3p = -3070.75*ztr - 18.126 &
& + (17.27039*ztr + 2.81197) * zsqrt &
& + (-44.99486*ztr - 0.09984) * zsal
! CONSTANT FOR SILICATE, MILLERO (1995)
zcksi = -8904.2*ztr + 117.400 - 19.334*zlogt &
& + (-458.79*ztr + 3.5913) * zisqrt &
& + (188.74*ztr - 1.5998) * zis &
& + (-12.1652*ztr + 0.07871) * zis2 &
& + LOG(1.0 - 0.001005*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
! CONVERT FROM DIFFERENT PH SCALES
total2free = 1.0/(1.0 + zst/zcks)
free2SWS = 1. + zst/zcks + zft/(zckf*total2free)
total2SWS = total2free * free2SWS
SWS2total = 1.0 / total2SWS
! K1, K2 OF CARBONIC ACID, KB OF BORIC ACID, KW (H2O) (LIT.?)
zak1 = 10**(zck1) * total2SWS
zak2 = 10**(zck2) * total2SWS
zakb = EXP( zckb ) * total2SWS
zakw = EXP( zckw )
zaksp1 = 10**(zaksp0)
zak1p = exp( zck1p )
zak2p = exp( zck2p )
zak3p = exp( zck3p )
zaksi = exp( zcksi )
zckf = zckf * total2SWS
! 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 * zcpexp
! KB OF BORIC ACID, K1,K2 OF CARBONIC ACID PRESSURE
! CORRECTION AFTER CULBERSON AND PYTKOWICZ (1968)
! (CF. BROECKER ET AL., 1982)
zbuf1 = - ( devk10 + devk20 * ztc + devk30 * ztc * ztc )
zbuf2 = 0.5 * ( devk40 + devk50 * ztc )
ak13(ji,jj,jk) = zak1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk11 + devk21 * ztc + devk31 * ztc * ztc )
zbuf2 = 0.5 * ( devk41 + devk51 * ztc )
ak23(ji,jj,jk) = zak2 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk12 + devk22 * ztc + devk32 * ztc * ztc )
zbuf2 = 0.5 * ( devk42 + devk52 * ztc )
akb3(ji,jj,jk) = zakb * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk13 + devk23 * ztc + devk33 * ztc * ztc )
zbuf2 = 0.5 * ( devk43 + devk53 * ztc )
akw3(ji,jj,jk) = zakw * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk14 + devk24 * ztc + devk34 * ztc * ztc )
zbuf2 = 0.5 * ( devk44 + devk54 * ztc )
aks3(ji,jj,jk) = zcks * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk15 + devk25 * ztc + devk35 * ztc * ztc )
zbuf2 = 0.5 * ( devk45 + devk55 * ztc )
akf3(ji,jj,jk) = zckf * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk17 + devk27 * ztc + devk37 * ztc * ztc )
zbuf2 = 0.5 * ( devk47 + devk57 * ztc )
ak1p3(ji,jj,jk) = zak1p * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk18 + devk28 * ztc + devk38 * ztc * ztc )
zbuf2 = 0.5 * ( devk48 + devk58 * ztc )
ak2p3(ji,jj,jk) = zak2p * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk19 + devk29 * ztc + devk39 * ztc * ztc )
zbuf2 = 0.5 * ( devk49 + devk59 * ztc )
ak3p3(ji,jj,jk) = zak3p * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
zbuf1 = - ( devk110 + devk210 * ztc + devk310 * ztc * ztc )
zbuf2 = 0.5 * ( devk410 + devk510 * ztc )
aksi3(ji,jj,jk) = zaksi * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
! CONVERT FROM DIFFERENT PH SCALES
total2free = 1.0/(1.0 + zst/aks3(ji,jj,jk))
free2SWS = 1. + zst/aks3(ji,jj,jk) + zft/akf3(ji,jj,jk)
total2SWS = total2free * free2SWS
SWS2total = 1.0 / total2SWS
! Convert to total scale
ak13(ji,jj,jk) = ak13(ji,jj,jk) * SWS2total
ak23(ji,jj,jk) = ak23(ji,jj,jk) * SWS2total
akb3(ji,jj,jk) = akb3(ji,jj,jk) * SWS2total
akw3(ji,jj,jk) = akw3(ji,jj,jk) * SWS2total
ak1p3(ji,jj,jk) = ak1p3(ji,jj,jk) * SWS2total
ak2p3(ji,jj,jk) = ak2p3(ji,jj,jk) * SWS2total
ak3p3(ji,jj,jk) = ak3p3(ji,jj,jk) * SWS2total
aksi3(ji,jj,jk) = aksi3(ji,jj,jk) * SWS2total
akf3(ji,jj,jk) = akf3(ji,jj,jk) / total2free
! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE
! AS FUNCTION OF PRESSURE FOLLOWING MILLERO
! (P. 1285) AND BERNER (1976)
zbuf1 = - ( devk16 + devk26 * ztc + devk36 * ztc * ztc )
zbuf2 = 0.5 * ( devk46 + devk56 * ztc )
aksp(ji,jj,jk) = zaksp1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 )
! TOTAL F, S, and BORATE CONCENTR. [MOLES/L]
borat(ji,jj,jk) = 0.0002414 * zcl / 10.811
sulfat(ji,jj,jk) = zst
fluorid(ji,jj,jk) = zft
! 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 / ztkel )
! Liu and Millero (1999) only valid 5 - 50 degC
ztkel1 = MAX( 5. , tempis(ji,jj,jk) ) + 273.16
fesol(ji,jj,jk,1) = 10**(-13.486 - 0.1856* zis**0.5 + 0.3073*zis + 5254.0/ztkel1)
fesol(ji,jj,jk,2) = 10**(2.517 - 0.8885*zis**0.5 + 0.2139 * zis - 1320.0/ztkel1 )
fesol(ji,jj,jk,3) = 10**(0.4511 - 0.3305*zis**0.5 - 1996.0/ztkel1 )
fesol(ji,jj,jk,4) = 10**(-0.2965 - 0.7881*zis**0.5 - 4086.0/ztkel1 )
fesol(ji,jj,jk,5) = 10**(4.4466 - 0.8505*zis**0.5 - 7980.0/ztkel1 )
END_3D
!
IF( ln_timing ) CALL timing_stop('p4z_che')
!
END SUBROUTINE p4z_che
SUBROUTINE ahini_for_at(p_hini, Kbb )
!!---------------------------------------------------------------------
!! *** ROUTINE ahini_for_at ***
!!
!! Subroutine returns the root for the 2nd order approximation of the
!! DIC -- B_T -- A_CB equation for [H+] (reformulated as a cubic
!! polynomial) around the local minimum, if it exists.
!! Returns * 1E-03_wp if p_alkcb <= 0
!! * 1E-10_wp if p_alkcb >= 2*p_dictot + p_bortot
!! * 1E-07_wp if 0 < p_alkcb < 2*p_dictot + p_bortot
!! and the 2nd order approximation does not have
!! a solution
!!---------------------------------------------------------------------
REAL(wp), DIMENSION(jpi,jpj,jpk), INTENT(OUT) :: p_hini
INTEGER, INTENT(in) :: Kbb ! time level indices
INTEGER :: ji, jj, jk
REAL(wp) :: zca1, zba1
REAL(wp) :: zd, zsqrtd, zhmin
REAL(wp) :: za2, za1, za0
REAL(wp) :: p_dictot, p_bortot, p_alkcb
!!---------------------------------------------------------------------
IF( ln_timing ) CALL timing_start('ahini_for_at')
!
DO_3D( nn_hls, nn_hls, nn_hls, nn_hls, 1, jpk )
p_alkcb = tr(ji,jj,jk,jptal,Kbb) * 1000. / (rhop(ji,jj,jk) + rtrn)
p_dictot = tr(ji,jj,jk,jpdic,Kbb) * 1000. / (rhop(ji,jj,jk) + rtrn)
p_bortot = borat(ji,jj,jk)
IF (p_alkcb <= 0.) THEN
p_hini(ji,jj,jk) = 1.e-3
ELSEIF (p_alkcb >= (2.*p_dictot + p_bortot)) THEN
p_hini(ji,jj,jk) = 1.e-10_wp
ELSE
zca1 = p_dictot/( p_alkcb + rtrn )
zba1 = p_bortot/ (p_alkcb + rtrn )
! Coefficients of the cubic polynomial
za2 = aKb3(ji,jj,jk)*(1. - zba1) + ak13(ji,jj,jk)*(1.-zca1)
za1 = ak13(ji,jj,jk)*akb3(ji,jj,jk)*(1. - zba1 - zca1) &
& + ak13(ji,jj,jk)*ak23(ji,jj,jk)*(1. - (zca1+zca1))
za0 = ak13(ji,jj,jk)*ak23(ji,jj,jk)*akb3(ji,jj,jk)*(1. - zba1 - (zca1+zca1))
! Taylor expansion around the minimum
zd = za2*za2 - 3.*za1 ! Discriminant of the quadratic equation
! for the minimum close to the root
IF(zd > 0.) THEN ! If the discriminant is positive
zsqrtd = SQRT(zd)
IF(za2 < 0) THEN
zhmin = (-za2 + zsqrtd)/3.
ELSE
zhmin = -za1/(za2 + zsqrtd)
ENDIF
p_hini(ji,jj,jk) = zhmin + SQRT(-(za0 + zhmin*(za1 + zhmin*(za2 + zhmin)))/zsqrtd)
ELSE
p_hini(ji,jj,jk) = 1.e-7
ENDIF
!
ENDIF
END_3D
!
IF( ln_timing ) CALL timing_stop('ahini_for_at')
!
END SUBROUTINE ahini_for_at
!===============================================================================
SUBROUTINE anw_infsup( p_alknw_inf, p_alknw_sup, Kbb )
! Subroutine returns the lower and upper bounds of "non-water-selfionization"
! contributions to total alkalinity (the infimum and the supremum), i.e
! inf(TA - [OH-] + [H+]) and sup(TA - [OH-] + [H+])
! Argument variables
REAL(wp), DIMENSION(jpi,jpj,jpk), INTENT(OUT) :: p_alknw_inf
REAL(wp), DIMENSION(jpi,jpj,jpk), INTENT(OUT) :: p_alknw_sup
INTEGER, INTENT(in) :: Kbb ! time level indices
p_alknw_inf(:,:,:) = -tr(:,:,:,jppo4,Kbb) * 1000. / (rhop(:,:,:) + rtrn) - sulfat(:,:,:) &
& - fluorid(:,:,:)
p_alknw_sup(:,:,:) = (2. * tr(:,:,:,jpdic,Kbb) + 2. * tr(:,:,:,jppo4,Kbb) + tr(:,:,:,jpsil,Kbb) ) &
& * 1000. / (rhop(:,:,:) + rtrn) + borat(:,:,:)
END SUBROUTINE anw_infsup
SUBROUTINE solve_at_general( p_hini, zhi, Kbb )
! Universal pH solver that converges from any given initial value,
! determines upper an lower bounds for the solution if required
! Argument variables
!--------------------
REAL(wp), DIMENSION(jpi,jpj,jpk), INTENT(IN) :: p_hini
REAL(wp), DIMENSION(jpi,jpj,jpk), INTENT(OUT) :: zhi
INTEGER, INTENT(in) :: Kbb ! time level indices
! Local variables
!-----------------
INTEGER :: ji, jj, jk, jn
REAL(wp) :: zh_ini, zh, zh_prev, zh_lnfactor
REAL(wp) :: zdelta, zh_delta
REAL(wp) :: zeqn, zdeqndh, zalka
REAL(wp) :: aphscale
REAL(wp) :: znumer_dic, zdnumer_dic, zdenom_dic, zalk_dic, zdalk_dic
REAL(wp) :: znumer_bor, zdnumer_bor, zdenom_bor, zalk_bor, zdalk_bor
REAL(wp) :: znumer_po4, zdnumer_po4, zdenom_po4, zalk_po4, zdalk_po4
REAL(wp) :: znumer_sil, zdnumer_sil, zdenom_sil, zalk_sil, zdalk_sil
REAL(wp) :: znumer_so4, zdnumer_so4, zdenom_so4, zalk_so4, zdalk_so4
REAL(wp) :: znumer_flu, zdnumer_flu, zdenom_flu, zalk_flu, zdalk_flu
REAL(wp) :: zalk_wat, zdalk_wat
REAL(wp) :: zfact, p_alktot, zdic, zbot, zpt, zst, zft, zsit
LOGICAL :: l_exitnow
REAL(wp), PARAMETER :: pz_exp_threshold = 1.0
REAL(wp), DIMENSION(jpi,jpj,jpk) :: zalknw_inf, zalknw_sup, rmask, zh_min, zh_max, zeqn_absmin
IF( ln_timing ) CALL timing_start('solve_at_general')
CALL anw_infsup( zalknw_inf, zalknw_sup, Kbb )
rmask(:,:,:) = tmask(:,:,:)
zhi(:,:,:) = 0.
! TOTAL H+ scale: conversion factor for Htot = aphscale * Hfree
DO_3D( nn_hls, nn_hls, nn_hls, nn_hls, 1, jpk )
IF (rmask(ji,jj,jk) == 1.) THEN
p_alktot = tr(ji,jj,jk,jptal,Kbb) * 1000. / (rhop(ji,jj,jk) + rtrn)
aphscale = 1. + sulfat(ji,jj,jk)/aks3(ji,jj,jk)
zh_ini = p_hini(ji,jj,jk)
zdelta = (p_alktot-zalknw_inf(ji,jj,jk))**2 + 4.*akw3(ji,jj,jk)/aphscale
IF(p_alktot >= zalknw_inf(ji,jj,jk)) THEN
zh_min(ji,jj,jk) = 2.*akw3(ji,jj,jk) /( p_alktot-zalknw_inf(ji,jj,jk) + SQRT(zdelta) )
ELSE
zh_min(ji,jj,jk) = aphscale*(-(p_alktot-zalknw_inf(ji,jj,jk)) + SQRT(zdelta) ) / 2.
ENDIF
zdelta = (p_alktot-zalknw_sup(ji,jj,jk))**2 + 4.*akw3(ji,jj,jk)/aphscale
IF(p_alktot <= zalknw_sup(ji,jj,jk)) THEN
zh_max(ji,jj,jk) = aphscale*(-(p_alktot-zalknw_sup(ji,jj,jk)) + SQRT(zdelta) ) / 2.
ELSE
zh_max(ji,jj,jk) = 2.*akw3(ji,jj,jk) /( p_alktot-zalknw_sup(ji,jj,jk) + SQRT(zdelta) )
ENDIF
zhi(ji,jj,jk) = MAX(MIN(zh_max(ji,jj,jk), zh_ini), zh_min(ji,jj,jk))
ENDIF
END_3D
zeqn_absmin(:,:,:) = HUGE(1._wp)
DO jn = 1, jp_maxniter_atgen
DO_3D( nn_hls, nn_hls, nn_hls, nn_hls, 1, jpk )
IF (rmask(ji,jj,jk) == 1.) THEN
zfact = rhop(ji,jj,jk) / 1000. + rtrn
p_alktot = tr(ji,jj,jk,jptal,Kbb) / zfact
zdic = tr(ji,jj,jk,jpdic,Kbb) / zfact
zbot = borat(ji,jj,jk)
zpt = tr(ji,jj,jk,jppo4,Kbb) / zfact * po4r
zsit = tr(ji,jj,jk,jpsil,Kbb) / zfact
zst = sulfat (ji,jj,jk)
zft = fluorid(ji,jj,jk)
aphscale = 1. + sulfat(ji,jj,jk)/aks3(ji,jj,jk)
zh = zhi(ji,jj,jk)
zh_prev = zh
! H2CO3 - HCO3 - CO3 : n=2, m=0
znumer_dic = 2.*ak13(ji,jj,jk)*ak23(ji,jj,jk) + zh*ak13(ji,jj,jk)
zdenom_dic = ak13(ji,jj,jk)*ak23(ji,jj,jk) + zh*(ak13(ji,jj,jk) + zh)
zalk_dic = zdic * (znumer_dic/zdenom_dic)
zdnumer_dic = ak13(ji,jj,jk)*ak13(ji,jj,jk)*ak23(ji,jj,jk) + zh &
*(4.*ak13(ji,jj,jk)*ak23(ji,jj,jk) + zh*ak13(ji,jj,jk))
zdalk_dic = -zdic*(zdnumer_dic/zdenom_dic**2)
! B(OH)3 - B(OH)4 : n=1, m=0
znumer_bor = akb3(ji,jj,jk)
zdenom_bor = akb3(ji,jj,jk) + zh
zalk_bor = zbot * (znumer_bor/zdenom_bor)
zdnumer_bor = akb3(ji,jj,jk)
zdalk_bor = -zbot*(zdnumer_bor/zdenom_bor**2)
! H3PO4 - H2PO4 - HPO4 - PO4 : n=3, m=1
znumer_po4 = 3.*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk)*ak3p3(ji,jj,jk) &
& + zh*(2.*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk) + zh* ak1p3(ji,jj,jk))
zdenom_po4 = ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk)*ak3p3(ji,jj,jk) &
& + zh*( ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk) + zh*(ak1p3(ji,jj,jk) + zh))
zalk_po4 = zpt * (znumer_po4/zdenom_po4 - 1.) ! Zero level of H3PO4 = 1
zdnumer_po4 = ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk)*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk)*ak3p3(ji,jj,jk) &
& + zh*(4.*ak1p3(ji,jj,jk)*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk)*ak3p3(ji,jj,jk) &
& + zh*(9.*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk)*ak3p3(ji,jj,jk) &
& + ak1p3(ji,jj,jk)*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk) &
& + zh*(4.*ak1p3(ji,jj,jk)*ak2p3(ji,jj,jk) + zh * ak1p3(ji,jj,jk) ) ) )
zdalk_po4 = -zpt * (zdnumer_po4/zdenom_po4**2)
! H4SiO4 - H3SiO4 : n=1, m=0
znumer_sil = aksi3(ji,jj,jk)
zdenom_sil = aksi3(ji,jj,jk) + zh
zalk_sil = zsit * (znumer_sil/zdenom_sil)
zdnumer_sil = aksi3(ji,jj,jk)
zdalk_sil = -zsit * (zdnumer_sil/zdenom_sil**2)
! HSO4 - SO4 : n=1, m=1
aphscale = 1.0 + zst/aks3(ji,jj,jk)
znumer_so4 = aks3(ji,jj,jk) * aphscale
zdenom_so4 = aks3(ji,jj,jk) * aphscale + zh
zalk_so4 = zst * (znumer_so4/zdenom_so4 - 1.)
zdnumer_so4 = aks3(ji,jj,jk)
zdalk_so4 = -zst * (zdnumer_so4/zdenom_so4**2)
! HF - F : n=1, m=1
znumer_flu = akf3(ji,jj,jk)
zdenom_flu = akf3(ji,jj,jk) + zh
zalk_flu = zft * (znumer_flu/zdenom_flu - 1.)
zdnumer_flu = akf3(ji,jj,jk)
zdalk_flu = -zft * (zdnumer_flu/zdenom_flu**2)
! H2O - OH
aphscale = 1.0 + zst/aks3(ji,jj,jk)
zalk_wat = akw3(ji,jj,jk)/zh - zh/aphscale
zdalk_wat = -akw3(ji,jj,jk)/zh**2 - 1./aphscale
! CALCULATE [ALK]([CO3--], [HCO3-])
zeqn = zalk_dic + zalk_bor + zalk_po4 + zalk_sil &
& + zalk_so4 + zalk_flu &
& + zalk_wat - p_alktot
zalka = p_alktot - (zalk_bor + zalk_po4 + zalk_sil &
& + zalk_so4 + zalk_flu + zalk_wat)
zdeqndh = zdalk_dic + zdalk_bor + zdalk_po4 + zdalk_sil &
& + zdalk_so4 + zdalk_flu + zdalk_wat
! Adapt bracketing interval
IF(zeqn > 0._wp) THEN
zh_min(ji,jj,jk) = zh_prev
ELSEIF(zeqn < 0._wp) THEN
zh_max(ji,jj,jk) = zh_prev
ENDIF
IF(ABS(zeqn) >= 0.5_wp*zeqn_absmin(ji,jj,jk)) THEN
! if the function evaluation at the current point is
! not decreasing faster than with a bisection step (at least linearly)
! in absolute value take one bisection step on [ph_min, ph_max]
! ph_new = (ph_min + ph_max)/2d0
!
! In terms of [H]_new:
! [H]_new = 10**(-ph_new)
! = 10**(-(ph_min + ph_max)/2d0)
! = SQRT(10**(-(ph_min + phmax)))
! = SQRT(zh_max * zh_min)
zh = SQRT(zh_max(ji,jj,jk) * zh_min(ji,jj,jk))
zh_lnfactor = (zh - zh_prev)/zh_prev ! Required to test convergence below
ELSE
! dzeqn/dpH = dzeqn/d[H] * d[H]/dpH
! = -zdeqndh * LOG(10) * [H]
! \Delta pH = -zeqn/(zdeqndh*d[H]/dpH) = zeqn/(zdeqndh*[H]*LOG(10))
!
! pH_new = pH_old + \deltapH
!
! [H]_new = 10**(-pH_new)
! = 10**(-pH_old - \Delta pH)
! = [H]_old * 10**(-zeqn/(zdeqndh*[H]_old*LOG(10)))
! = [H]_old * EXP(-LOG(10)*zeqn/(zdeqndh*[H]_old*LOG(10)))
! = [H]_old * EXP(-zeqn/(zdeqndh*[H]_old))
zh_lnfactor = -zeqn/(zdeqndh*zh_prev)
IF(ABS(zh_lnfactor) > pz_exp_threshold) THEN
zh = zh_prev*EXP(zh_lnfactor)
ELSE
zh_delta = zh_lnfactor*zh_prev
zh = zh_prev + zh_delta
ENDIF
IF( zh < zh_min(ji,jj,jk) ) THEN
! if [H]_new < [H]_min
! i.e., if ph_new > ph_max then
! take one bisection step on [ph_prev, ph_max]
! ph_new = (ph_prev + ph_max)/2d0
! In terms of [H]_new:
! [H]_new = 10**(-ph_new)
! = 10**(-(ph_prev + ph_max)/2d0)
! = SQRT(10**(-(ph_prev + phmax)))
! = SQRT([H]_old*10**(-ph_max))
! = SQRT([H]_old * zh_min)
zh = SQRT(zh_prev * zh_min(ji,jj,jk))
zh_lnfactor = (zh - zh_prev)/zh_prev ! Required to test convergence below
ENDIF
IF( zh > zh_max(ji,jj,jk) ) THEN
! if [H]_new > [H]_max
! i.e., if ph_new < ph_min, then
! take one bisection step on [ph_min, ph_prev]
! ph_new = (ph_prev + ph_min)/2d0
! In terms of [H]_new:
! [H]_new = 10**(-ph_new)
! = 10**(-(ph_prev + ph_min)/2d0)
! = SQRT(10**(-(ph_prev + ph_min)))
! = SQRT([H]_old*10**(-ph_min))
! = SQRT([H]_old * zhmax)
zh = SQRT(zh_prev * zh_max(ji,jj,jk))
zh_lnfactor = (zh - zh_prev)/zh_prev ! Required to test convergence below
ENDIF
ENDIF
zeqn_absmin(ji,jj,jk) = MIN( ABS(zeqn), zeqn_absmin(ji,jj,jk))
! Stop iterations once |\delta{[H]}/[H]| < rdel
! <=> |(zh - zh_prev)/zh_prev| = |EXP(-zeqn/(zdeqndh*zh_prev)) -1| < rdel
! |EXP(-zeqn/(zdeqndh*zh_prev)) -1| ~ |zeqn/(zdeqndh*zh_prev)|
! Alternatively:
! |\Delta pH| = |zeqn/(zdeqndh*zh_prev*LOG(10))|
! ~ 1/LOG(10) * |\Delta [H]|/[H]
! < 1/LOG(10) * rdel
! Hence |zeqn/(zdeqndh*zh)| < rdel
! rdel <-- pp_rdel_ah_target
l_exitnow = (ABS(zh_lnfactor) < pp_rdel_ah_target)
IF(l_exitnow) THEN
rmask(ji,jj,jk) = 0.
ENDIF
zhi(ji,jj,jk) = zh
IF(jn >= jp_maxniter_atgen) THEN
zhi(ji,jj,jk) = -1._wp
ENDIF
ENDIF
END_3D
END DO
!
IF( ln_timing ) CALL timing_stop('solve_at_general')
!
END SUBROUTINE solve_at_general
INTEGER FUNCTION p4z_che_alloc()
!!----------------------------------------------------------------------
!! *** ROUTINE p4z_che_alloc ***
!!----------------------------------------------------------------------
INTEGER :: ierr(3) ! Local variables
!!----------------------------------------------------------------------
ierr(:) = 0
ALLOCATE( sio3eq(jpi,jpj,jpk), fekeq(jpi,jpj,jpk), chemc(jpi,jpj,3), chemo2(jpi,jpj,jpk), STAT=ierr(1) )
ALLOCATE( akb3(jpi,jpj,jpk) , tempis(jpi, jpj, jpk), &
& akw3(jpi,jpj,jpk) , borat (jpi,jpj,jpk) , &
& aks3(jpi,jpj,jpk) , akf3(jpi,jpj,jpk) , &
& ak1p3(jpi,jpj,jpk) , ak2p3(jpi,jpj,jpk) , &
& ak3p3(jpi,jpj,jpk) , aksi3(jpi,jpj,jpk) , &
& fluorid(jpi,jpj,jpk) , sulfat(jpi,jpj,jpk) , &
& salinprac(jpi,jpj,jpk), STAT=ierr(2) )
ALLOCATE( fesol(jpi,jpj,jpk,5), STAT=ierr(3) )
!* Variable for chemistry of the CO2 cycle
p4z_che_alloc = MAXVAL( ierr )
!
IF( p4z_che_alloc /= 0 ) CALL ctl_stop( 'STOP', 'p4z_che_alloc : failed to allocate arrays.' )
!
END FUNCTION p4z_che_alloc
!!======================================================================
END MODULE p4zche