| 1 | MODULE p4zche |
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| 2 | !!====================================================================== |
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| 3 | !! *** MODULE p4zche *** |
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| 4 | !! TOP : PISCES Sea water chemistry computed following OCMIP protocol |
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| 5 | !!====================================================================== |
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| 6 | !! History : OPA ! 1988 (E. Maier-Reimer) Original code |
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| 7 | !! - ! 1998 (O. Aumont) addition |
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| 8 | !! - ! 1999 (C. Le Quere) modification |
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| 9 | !! NEMO 1.0 ! 2004 (O. Aumont) modification |
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| 10 | !! - ! 2006 (R. Gangsto) modification |
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| 11 | !! 2.0 ! 2007-12 (C. Ethe, G. Madec) F90 |
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| 12 | !!---------------------------------------------------------------------- |
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| 13 | #if defined key_pisces |
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| 14 | !!---------------------------------------------------------------------- |
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| 15 | !! 'key_pisces' PISCES bio-model |
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| 16 | !!---------------------------------------------------------------------- |
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| 17 | !! p4z_che : Sea water chemistry computed following OCMIP protocol |
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| 18 | !!---------------------------------------------------------------------- |
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| 19 | USE oce_trc ! |
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| 20 | USE trc ! |
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| 21 | USE sms_pisces ! |
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| 22 | USE lib_mpp ! MPP library |
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| 23 | |
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| 24 | IMPLICIT NONE |
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| 25 | PRIVATE |
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| 26 | |
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| 27 | PUBLIC p4z_che ! |
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| 28 | PUBLIC p4z_che_alloc ! |
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| 29 | |
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| 30 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: sio3eq ! chemistry of Si |
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| 31 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: fekeq ! chemistry of Fe |
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| 32 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: chemc ! Solubilities of O2 and CO2 |
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| 33 | |
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| 34 | REAL(wp) :: salchl = 1._wp / 1.80655_wp ! conversion factor for salinity --> chlorinity (Wooster et al. 1969) |
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| 35 | |
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| 36 | REAL(wp) :: akcc1 = -171.9065_wp ! coeff. for apparent solubility equilibrium |
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| 37 | REAL(wp) :: akcc2 = -0.077993_wp ! Millero et al. 1995 from Mucci 1983 |
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| 38 | REAL(wp) :: akcc3 = 2839.319_wp ! |
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| 39 | REAL(wp) :: akcc4 = 71.595_wp ! |
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| 40 | REAL(wp) :: akcc5 = -0.77712_wp ! |
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| 41 | REAL(wp) :: akcc6 = 0.0028426_wp ! |
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| 42 | REAL(wp) :: akcc7 = 178.34_wp ! |
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| 43 | REAL(wp) :: akcc8 = -0.07711_wp ! |
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| 44 | REAL(wp) :: akcc9 = 0.0041249_wp ! |
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| 45 | |
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| 46 | REAL(wp) :: rgas = 83.143_wp ! universal gas constants |
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| 47 | REAL(wp) :: oxyco = 1._wp / 22.4144_wp |
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| 48 | |
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| 49 | REAL(wp) :: bor1 = 0.00023_wp ! borat constants |
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| 50 | REAL(wp) :: bor2 = 1._wp / 10.82_wp |
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| 51 | |
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| 52 | REAL(wp) :: ca0 = -162.8301_wp |
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| 53 | REAL(wp) :: ca1 = 218.2968_wp |
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| 54 | REAL(wp) :: ca2 = 90.9241_wp |
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| 55 | REAL(wp) :: ca3 = -1.47696_wp |
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| 56 | REAL(wp) :: ca4 = 0.025695_wp |
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| 57 | REAL(wp) :: ca5 = -0.025225_wp |
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| 58 | REAL(wp) :: ca6 = 0.0049867_wp |
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| 59 | |
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| 60 | REAL(wp) :: c10 = -3670.7_wp ! coeff. for 1. dissoc. of carbonic acid (Edmond and Gieskes, 1970) |
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| 61 | REAL(wp) :: c11 = 62.008_wp |
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| 62 | REAL(wp) :: c12 = -9.7944_wp |
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| 63 | REAL(wp) :: c13 = 0.0118_wp |
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| 64 | REAL(wp) :: c14 = -0.000116_wp |
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| 65 | |
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| 66 | REAL(wp) :: & ! coeff. for 2. dissoc. of carbonic acid (Millero, 1995) |
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| 67 | c20 = -1394.7 , & |
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| 68 | c21 = -4.777 , & |
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| 69 | c22 = 0.0184 , & |
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| 70 | c23 = -0.000118 |
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| 71 | |
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| 72 | REAL(wp) :: & ! constants for calculate concentrations |
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| 73 | st1 = 0.14 , & ! for sulfate (Morris & Riley 1966) |
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| 74 | st2 = 1./96.062, & |
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| 75 | ks0 = 141.328 , & |
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| 76 | ks1 = -4276.1 , & |
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| 77 | ks2 = -23.093 , & |
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| 78 | ks3 = -13856. , & |
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| 79 | ks4 = 324.57 , & |
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| 80 | ks5 = -47.986 , & |
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| 81 | ks6 = 35474. , & |
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| 82 | ks7 = -771.54 , & |
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| 83 | ks8 = 114.723 , & |
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| 84 | ks9 = -2698. , & |
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| 85 | ks10 = 1776. , & |
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| 86 | ks11 = 1. , & |
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| 87 | ks12 = -0.001005 |
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| 88 | |
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| 89 | REAL(wp) :: & ! constants for calculate concentrations |
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| 90 | ft1 = 0.000067 , & ! fluorides (Dickson & Riley 1979 ) |
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| 91 | ft2 = 1./18.9984 , & |
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| 92 | kf0 = -12.641 , & |
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| 93 | kf1 = 1590.2 , & |
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| 94 | kf2 = 1.525 , & |
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| 95 | kf3 = 1.0 , & |
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| 96 | kf4 =-0.001005 |
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| 97 | |
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| 98 | REAL(wp) :: & ! coeff. for 1. dissoc. of boric acid (Dickson and Goyet, 1994) |
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| 99 | cb0 = -8966.90, & |
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| 100 | cb1 = -2890.53, & |
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| 101 | cb2 = -77.942 , & |
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| 102 | cb3 = 1.728 , & |
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| 103 | cb4 = -0.0996 , & |
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| 104 | cb5 = 148.0248, & |
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| 105 | cb6 = 137.1942, & |
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| 106 | cb7 = 1.62142 , & |
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| 107 | cb8 = -24.4344, & |
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| 108 | cb9 = -25.085 , & |
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| 109 | cb10 = -0.2474 , & |
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| 110 | cb11 = 0.053105 |
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| 111 | |
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| 112 | REAL(wp) :: & ! coeff. for dissoc. of water (Dickson and Riley, 1979 ) |
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| 113 | cw0 = -13847.26 , & |
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| 114 | cw1 = 148.9652 , & |
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| 115 | cw2 = -23.6521 , & |
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| 116 | cw3 = 118.67 , & |
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| 117 | cw4 = -5.977 , & |
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| 118 | cw5 = 1.0495 , & |
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| 119 | cw6 = -0.01615 |
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| 120 | |
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| 121 | REAL(wp) :: & ! volumetric solubility constants for o2 in ml/l (Weiss, 1974) |
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| 122 | ox0 = -58.3877 , & |
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| 123 | ox1 = 85.8079 , & |
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| 124 | ox2 = 23.8439 , & |
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| 125 | ox3 = -0.034892 , & |
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| 126 | ox4 = 0.015568 , & |
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| 127 | ox5 = -0.0019387 |
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| 128 | |
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| 129 | REAL(wp), DIMENSION(5) :: & ! coeff. for seawater pressure correction |
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| 130 | devk1, devk2, devk3, & ! (millero 95) |
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| 131 | devk4, devk5 |
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| 132 | |
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| 133 | DATA devk1 / -25.5 , -15.82 , -29.48 , -25.60 , -48.76 / |
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| 134 | DATA devk2 / 0.1271 , -0.0219 , 0.1622 , 0.2324 , 0.5304 / |
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| 135 | DATA devk3 / 0. , 0. , 2.608E-3, -3.6246E-3, 0. / |
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| 136 | DATA devk4 / -3.08E-3 , 1.13E-3 , -2.84E-3, -5.13E-3 , -11.76E-3 / |
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| 137 | DATA devk5 / 0.0877E-3, -0.1475E-3, 0. , 0.0794E-3 , 0.3692E-3 / |
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| 138 | |
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| 139 | !!* Substitution |
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| 140 | #include "top_substitute.h90" |
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| 141 | !!---------------------------------------------------------------------- |
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| 142 | !! NEMO/TOP 3.3 , NEMO Consortium (2010) |
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| 143 | !! $Id$ |
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| 144 | !! Software governed by the CeCILL licence (NEMOGCM/NEMO_CeCILL.txt) |
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| 145 | !!---------------------------------------------------------------------- |
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| 146 | CONTAINS |
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| 147 | |
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| 148 | SUBROUTINE p4z_che |
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| 149 | !!--------------------------------------------------------------------- |
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| 150 | !! *** ROUTINE p4z_che *** |
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| 151 | !! |
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| 152 | !! ** Purpose : Sea water chemistry computed following OCMIP protocol |
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| 153 | !! |
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| 154 | !! ** Method : - ... |
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| 155 | !!--------------------------------------------------------------------- |
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| 156 | INTEGER :: ji, jj, jk |
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| 157 | REAL(wp) :: ztkel, zsal , zqtt , zbuf1 , zbuf2 |
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| 158 | REAL(wp) :: zpres, ztc , zcl , zcpexp, zoxy , zcpexp2 |
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| 159 | REAL(wp) :: zsqrt, ztr , zlogt , zcek1 |
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| 160 | REAL(wp) :: zlqtt, zqtt2, zsal15, zis , zis2 , zisqrt |
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| 161 | REAL(wp) :: zckb , zck1 , zck2 , zckw , zak1 , zak2 , zakb , zaksp0, zakw |
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| 162 | REAL(wp) :: zst , zft , zcks , zckf , zaksp1 |
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| 163 | !!--------------------------------------------------------------------- |
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| 164 | |
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| 165 | ! CHEMICAL CONSTANTS - SURFACE LAYER |
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| 166 | ! ---------------------------------- |
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| 167 | !CDIR NOVERRCHK |
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| 168 | DO jj = 1, jpj |
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| 169 | !CDIR NOVERRCHK |
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| 170 | DO ji = 1, jpi |
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| 171 | ! ! SET ABSOLUTE TEMPERATURE |
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| 172 | ztkel = tsn(ji,jj,1,jp_tem) + 273.16 |
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| 173 | zqtt = ztkel * 0.01 |
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| 174 | zqtt2 = zqtt * zqtt |
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| 175 | zsal = tsn(ji,jj,1,jp_sal) + (1.- tmask(ji,jj,1) ) * 35. |
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| 176 | zlqtt = LOG( zqtt ) |
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| 177 | |
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| 178 | ! ! LN(K0) OF SOLUBILITY OF CO2 (EQ. 12, WEISS, 1980) |
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| 179 | ! ! AND FOR THE ATMOSPHERE FOR NON IDEAL GAS |
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| 180 | zcek1 = ca0 + ca1 / zqtt + ca2 * zlqtt + ca3 * zqtt2 + zsal*( ca4 + ca5 * zqtt + ca6 * zqtt2 ) |
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| 181 | |
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| 182 | ! ! LN(K0) OF SOLUBILITY OF O2 and N2 (EQ. 4, WEISS, 1970) |
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| 183 | zoxy = ox0 + ox1 / zqtt + ox2 * zlqtt + zsal * ( ox3 + ox4 * zqtt + ox5 * zqtt2 ) |
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| 184 | |
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| 185 | ! ! SET SOLUBILITIES OF O2 AND CO2 |
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| 186 | chemc(ji,jj,1) = EXP( zcek1 ) * 1.e-6 * rhop(ji,jj,1) / 1000. |
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| 187 | chemc(ji,jj,2) = EXP( zoxy ) * oxyco |
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| 188 | |
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| 189 | END DO |
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| 190 | END DO |
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| 191 | |
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| 192 | ! CHEMICAL CONSTANTS - DEEP OCEAN |
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| 193 | ! ------------------------------- |
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| 194 | !CDIR NOVERRCHK |
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| 195 | DO jk = 1, jpk |
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| 196 | !CDIR NOVERRCHK |
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| 197 | DO jj = 1, jpj |
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| 198 | !CDIR NOVERRCHK |
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| 199 | DO ji = 1, jpi |
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| 200 | |
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| 201 | ! SET PRESSION |
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| 202 | zpres = 1.025e-1 * fsdept(ji,jj,jk) |
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| 203 | |
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| 204 | ! SET ABSOLUTE TEMPERATURE |
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| 205 | ztkel = tsn(ji,jj,jk,jp_tem) + 273.16 |
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| 206 | zqtt = ztkel * 0.01 |
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| 207 | zsal = tsn(ji,jj,jk,jp_sal) + ( 1.-tmask(ji,jj,jk) ) * 35. |
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| 208 | zsqrt = SQRT( zsal ) |
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| 209 | zsal15 = zsqrt * zsal |
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| 210 | zlogt = LOG( ztkel ) |
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| 211 | ztr = 1. / ztkel |
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| 212 | zis = 19.924 * zsal / ( 1000.- 1.005 * zsal ) |
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| 213 | zis2 = zis * zis |
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| 214 | zisqrt = SQRT( zis ) |
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| 215 | ztc = tsn(ji,jj,jk,jp_tem) + ( 1.- tmask(ji,jj,jk) ) * 20. |
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| 216 | |
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| 217 | ! CHLORINITY (WOOSTER ET AL., 1969) |
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| 218 | zcl = zsal * salchl |
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| 219 | |
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| 220 | ! TOTAL SULFATE CONCENTR. [MOLES/kg soln] |
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| 221 | zst = st1 * zcl * st2 |
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| 222 | |
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| 223 | ! TOTAL FLUORIDE CONCENTR. [MOLES/kg soln] |
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| 224 | zft = ft1 * zcl * ft2 |
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| 225 | |
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| 226 | ! DISSOCIATION CONSTANT FOR SULFATES on free H scale (Dickson 1990) |
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| 227 | zcks = EXP( ks1 * ztr + ks0 + ks2 * zlogt & |
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| 228 | & + ( ks3 * ztr + ks4 + ks5 * zlogt ) * zisqrt & |
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| 229 | & + ( ks6 * ztr + ks7 + ks8 * zlogt ) * zis & |
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| 230 | & + ks9 * ztr * zis * zisqrt + ks10 * ztr *zis2 + LOG( ks11 + ks12 *zsal ) ) |
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| 231 | |
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| 232 | ! DISSOCIATION CONSTANT FOR FLUORIDES on free H scale (Dickson and Riley 79) |
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| 233 | zckf = EXP( kf1 * ztr + kf0 + kf2 * zisqrt + LOG( kf3 + kf4 * zsal ) ) |
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| 234 | |
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| 235 | ! DISSOCIATION CONSTANT FOR CARBONATE AND BORATE |
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| 236 | zckb = ( cb0 + cb1 * zsqrt + cb2 * zsal + cb3 * zsal15 + cb4 * zsal * zsal ) * ztr & |
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| 237 | & + ( cb5 + cb6 * zsqrt + cb7 * zsal ) & |
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| 238 | & + ( cb8 + cb9 * zsqrt + cb10 * zsal ) * zlogt + cb11 * zsqrt * ztkel & |
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| 239 | & + LOG( ( 1.+ zst / zcks + zft / zckf ) / ( 1.+ zst / zcks ) ) |
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| 240 | |
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| 241 | zck1 = c10 * ztr + c11 + c12 * zlogt + c13 * zsal + c14 * zsal * zsal |
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| 242 | zck2 = c20 * ztr + c21 + c22 * zsal + c23 * zsal**2 |
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| 243 | |
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| 244 | ! PKW (H2O) (DICKSON AND RILEY, 1979) |
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| 245 | zckw = cw0 * ztr + cw1 + cw2 * zlogt + ( cw3 * ztr + cw4 + cw5 * zlogt ) * zsqrt + cw6 * zsal |
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| 246 | |
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| 247 | |
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| 248 | ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE IN SEAWATER |
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| 249 | ! (S=27-43, T=2-25 DEG C) at pres =0 (atmos. pressure) (MUCCI 1983) |
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| 250 | zaksp0 = akcc1 + akcc2 * ztkel + akcc3 * ztr + akcc4 * LOG10( ztkel ) & |
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| 251 | & + ( akcc5 + akcc6 * ztkel + akcc7 * ztr ) * zsqrt + akcc8 * zsal + akcc9 * zsal15 |
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| 252 | |
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| 253 | ! K1, K2 OF CARBONIC ACID, KB OF BORIC ACID, KW (H2O) (LIT.?) |
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| 254 | zak1 = 10**(zck1) |
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| 255 | zak2 = 10**(zck2) |
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| 256 | zakb = EXP( zckb ) |
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| 257 | zakw = EXP( zckw ) |
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| 258 | zaksp1 = 10**(zaksp0) |
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| 259 | |
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| 260 | ! FORMULA FOR CPEXP AFTER EDMOND & GIESKES (1970) |
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| 261 | ! (REFERENCE TO CULBERSON & PYTKOQICZ (1968) AS MADE |
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| 262 | ! IN BROECKER ET AL. (1982) IS INCORRECT; HERE RGAS IS |
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| 263 | ! TAKEN TENFOLD TO CORRECT FOR THE NOTATION OF pres IN |
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| 264 | ! DBAR INSTEAD OF BAR AND THE EXPRESSION FOR CPEXP IS |
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| 265 | ! MULTIPLIED BY LN(10.) TO ALLOW USE OF EXP-FUNCTION |
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| 266 | ! WITH BASIS E IN THE FORMULA FOR AKSPP (CF. EDMOND |
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| 267 | ! & GIESKES (1970), P. 1285-1286 (THE SMALL |
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| 268 | ! FORMULA ON P. 1286 IS RIGHT AND CONSISTENT WITH THE |
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| 269 | ! SIGN IN PARTIAL MOLAR VOLUME CHANGE AS SHOWN ON P. 1285)) |
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| 270 | zcpexp = zpres /(rgas*ztkel) |
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| 271 | zcpexp2 = zpres * zpres/(rgas*ztkel) |
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| 272 | |
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| 273 | ! KB OF BORIC ACID, K1,K2 OF CARBONIC ACID PRESSURE |
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| 274 | ! CORRECTION AFTER CULBERSON AND PYTKOWICZ (1968) |
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| 275 | ! (CF. BROECKER ET AL., 1982) |
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| 276 | |
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| 277 | zbuf1 = -(devk1(1)+devk2(1)*ztc+devk3(1)*ztc*ztc) |
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| 278 | zbuf2 = 0.5*(devk4(1)+devk5(1)*ztc) |
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| 279 | ak13(ji,jj,jk) = zak1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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| 280 | |
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| 281 | zbuf1 = - ( devk1(2) + devk2(2) * ztc + devk3(2) * ztc * ztc ) |
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| 282 | zbuf2 = 0.5 * ( devk4(2) + devk5(2) * ztc ) |
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| 283 | ak23(ji,jj,jk) = zak2 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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| 284 | |
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| 285 | zbuf1 = - ( devk1(3) + devk2(3) * ztc + devk3(3) * ztc * ztc ) |
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| 286 | zbuf2 = 0.5 * ( devk4(3) + devk5(3) * ztc ) |
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| 287 | akb3(ji,jj,jk) = zakb * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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| 288 | |
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| 289 | zbuf1 = - ( devk1(4) + devk2(4) * ztc + devk3(4) * ztc * ztc ) |
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| 290 | zbuf2 = 0.5 * ( devk4(4) + devk5(4) * ztc ) |
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| 291 | akw3(ji,jj,jk) = zakw * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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| 292 | |
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| 293 | |
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| 294 | ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE |
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| 295 | ! AS FUNCTION OF PRESSURE FOLLOWING MILLERO |
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| 296 | ! (P. 1285) AND BERNER (1976) |
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| 297 | zbuf1 = - ( devk1(5) + devk2(5) * ztc + devk3(5) * ztc * ztc ) |
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| 298 | zbuf2 = 0.5 * ( devk4(5) + devk5(5) * ztc ) |
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| 299 | aksp(ji,jj,jk) = zaksp1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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| 300 | |
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| 301 | |
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| 302 | ! TOTAL BORATE CONCENTR. [MOLES/L] |
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| 303 | borat(ji,jj,jk) = bor1 * zcl * bor2 |
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| 304 | |
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| 305 | ! Iron and SIO3 saturation concentration from ... |
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| 306 | sio3eq(ji,jj,jk) = EXP( LOG( 10.) * ( 6.44 - 968. / ztkel ) ) * 1.e-6 |
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| 307 | fekeq (ji,jj,jk) = 10**( 17.27 - 1565.7 / ( 273.15 + ztc ) ) |
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| 308 | |
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| 309 | END DO |
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| 310 | END DO |
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| 311 | END DO |
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| 312 | ! |
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| 313 | END SUBROUTINE p4z_che |
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| 314 | |
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| 315 | |
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| 316 | INTEGER FUNCTION p4z_che_alloc() |
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| 317 | !!---------------------------------------------------------------------- |
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| 318 | !! *** ROUTINE p4z_che_alloc *** |
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| 319 | !!---------------------------------------------------------------------- |
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| 320 | ALLOCATE( sio3eq(jpi,jpj,jpk) , fekeq(jpi,jpj,jpk) , chemc (jpi,jpj,2), STAT=p4z_che_alloc ) |
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| 321 | ! |
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| 322 | IF( p4z_che_alloc /= 0 ) CALL ctl_warn('p4z_che_alloc : failed to allocate arrays.') |
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| 323 | ! |
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| 324 | END FUNCTION p4z_che_alloc |
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| 325 | |
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| 326 | #else |
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| 327 | !!====================================================================== |
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| 328 | !! Dummy module : No PISCES bio-model |
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| 329 | !!====================================================================== |
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| 330 | CONTAINS |
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| 331 | SUBROUTINE p4z_che( kt ) ! Empty routine |
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| 332 | INTEGER, INTENT(in) :: kt |
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| 333 | WRITE(*,*) 'p4z_che: You should not have seen this print! error?', kt |
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| 334 | END SUBROUTINE p4z_che |
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| 335 | #endif |
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| 336 | |
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| 337 | !!====================================================================== |
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| 338 | END MODULE p4zche |
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