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 | !! ! 2011-02 (J. Simeon, J.Orr ) update O2 solubility constants |
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13 | !!---------------------------------------------------------------------- |
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14 | #if defined key_pisces |
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15 | !!---------------------------------------------------------------------- |
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16 | !! 'key_pisces' PISCES bio-model |
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17 | !!---------------------------------------------------------------------- |
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18 | !! p4z_che : Sea water chemistry computed following OCMIP protocol |
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19 | !!---------------------------------------------------------------------- |
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20 | USE oce_trc ! shared variables between ocean and passive tracers |
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21 | USE trc ! passive tracers common variables |
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22 | USE sms_pisces ! PISCES Source Minus Sink variables |
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23 | USE lib_mpp ! MPP library |
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24 | |
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25 | IMPLICIT NONE |
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26 | PRIVATE |
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27 | |
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28 | PUBLIC p4z_che ! |
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29 | PUBLIC p4z_che_alloc ! |
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30 | |
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31 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: sio3eq ! chemistry of Si |
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32 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: fekeq ! chemistry of Fe |
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33 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:) :: chemc ! Solubilities of O2 and CO2 |
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34 | REAL(wp), PUBLIC, ALLOCATABLE, SAVE, DIMENSION(:,:,:) :: chemo2 ! Solubilities of O2 and CO2 |
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35 | |
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36 | REAL(wp), PUBLIC :: atcox = 0.20946 ! units atm |
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37 | |
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38 | REAL(wp) :: salchl = 1. / 1.80655 ! conversion factor for salinity --> chlorinity (Wooster et al. 1969) |
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39 | REAL(wp) :: o2atm = 1. / ( 1000. * 0.20946 ) |
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40 | |
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41 | REAL(wp) :: akcc1 = -171.9065 ! coeff. for apparent solubility equilibrium |
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42 | REAL(wp) :: akcc2 = -0.077993 ! Millero et al. 1995 from Mucci 1983 |
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43 | REAL(wp) :: akcc3 = 2839.319 |
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44 | REAL(wp) :: akcc4 = 71.595 |
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45 | REAL(wp) :: akcc5 = -0.77712 |
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46 | REAL(wp) :: akcc6 = 0.00284263 |
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47 | REAL(wp) :: akcc7 = 178.34 |
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48 | REAL(wp) :: akcc8 = -0.07711 |
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49 | REAL(wp) :: akcc9 = 0.0041249 |
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50 | |
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51 | REAL(wp) :: rgas = 83.143 ! universal gas constants |
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52 | REAL(wp) :: oxyco = 1. / 22.4144 ! converts from liters of an ideal gas to moles |
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53 | |
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54 | REAL(wp) :: bor1 = 0.00023 ! borat constants |
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55 | REAL(wp) :: bor2 = 1. / 10.82 |
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56 | |
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57 | REAL(wp) :: ca0 = -162.8301 ! WEISS & PRICE 1980, units mol/(kg atm) |
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58 | REAL(wp) :: ca1 = 218.2968 |
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59 | REAL(wp) :: ca2 = 90.9241 |
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60 | REAL(wp) :: ca3 = -1.47696 |
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61 | REAL(wp) :: ca4 = 0.025695 |
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62 | REAL(wp) :: ca5 = -0.025225 |
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63 | REAL(wp) :: ca6 = 0.0049867 |
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64 | |
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65 | REAL(wp) :: c10 = -3670.7 ! Coeff. for 1. dissoc. of carbonic acid (Edmond and Gieskes, 1970) |
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66 | REAL(wp) :: c11 = 62.008 |
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67 | REAL(wp) :: c12 = -9.7944 |
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68 | REAL(wp) :: c13 = 0.0118 |
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69 | REAL(wp) :: c14 = -0.000116 |
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70 | |
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71 | REAL(wp) :: c20 = -1394.7 ! coeff. for 2. dissoc. of carbonic acid (Millero, 1995) |
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72 | REAL(wp) :: c21 = -4.777 |
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73 | REAL(wp) :: c22 = 0.0184 |
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74 | REAL(wp) :: c23 = -0.000118 |
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75 | |
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76 | REAL(wp) :: st1 = 0.14 ! constants for calculate concentrations for sulfate |
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77 | REAL(wp) :: st2 = 1./96.062 ! (Morris & Riley 1966) |
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78 | |
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79 | REAL(wp) :: ft1 = 0.000067 ! constants for calculate concentrations for fluorides |
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80 | REAL(wp) :: ft2 = 1./18.9984 ! (Dickson & Riley 1979 ) |
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81 | |
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82 | ! ! volumetric solubility constants for o2 in ml/L |
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83 | REAL(wp) :: ox0 = 2.00856 ! from Table 1 for Eq 8 of Garcia and Gordon, 1992. |
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84 | REAL(wp) :: ox1 = 3.22400 ! corrects for moisture and fugacity, but not total atmospheric pressure |
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85 | REAL(wp) :: ox2 = 3.99063 ! Original PISCES code noted this was a solubility, but |
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86 | REAL(wp) :: ox3 = 4.80299 ! was in fact a bunsen coefficient with units L-O2/(Lsw atm-O2) |
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87 | REAL(wp) :: ox4 = 9.78188e-1 ! Hence, need to divide EXP( zoxy ) by 1000, ml-O2 => L-O2 |
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88 | REAL(wp) :: ox5 = 1.71069 ! and atcox = 0.20946 to add the 1/atm dimension. |
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89 | REAL(wp) :: ox6 = -6.24097e-3 |
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90 | REAL(wp) :: ox7 = -6.93498e-3 |
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91 | REAL(wp) :: ox8 = -6.90358e-3 |
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92 | REAL(wp) :: ox9 = -4.29155e-3 |
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93 | REAL(wp) :: ox10 = -3.11680e-7 |
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94 | |
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95 | ! ! coeff. for seawater pressure correction : millero 95 |
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96 | ! ! AGRIF doesn't like the DATA instruction |
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97 | REAL(wp) :: devk11 = -25.5 |
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98 | REAL(wp) :: devk12 = -15.82 |
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99 | REAL(wp) :: devk13 = -29.48 |
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100 | REAL(wp) :: devk14 = -25.60 |
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101 | REAL(wp) :: devk15 = -48.76 |
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102 | ! |
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103 | REAL(wp) :: devk21 = 0.1271 |
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104 | REAL(wp) :: devk22 = -0.0219 |
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105 | REAL(wp) :: devk23 = 0.1622 |
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106 | REAL(wp) :: devk24 = 0.2324 |
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107 | REAL(wp) :: devk25 = 0.5304 |
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108 | ! |
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109 | REAL(wp) :: devk31 = 0. |
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110 | REAL(wp) :: devk32 = 0. |
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111 | REAL(wp) :: devk33 = 2.608E-3 |
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112 | REAL(wp) :: devk34 = -3.6246E-3 |
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113 | REAL(wp) :: devk35 = 0. |
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114 | ! |
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115 | REAL(wp) :: devk41 = -3.08E-3 |
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116 | REAL(wp) :: devk42 = 1.13E-3 |
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117 | REAL(wp) :: devk43 = -2.84E-3 |
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118 | REAL(wp) :: devk44 = -5.13E-3 |
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119 | REAL(wp) :: devk45 = -11.76E-3 |
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120 | ! |
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121 | REAL(wp) :: devk51 = 0.0877E-3 |
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122 | REAL(wp) :: devk52 = -0.1475E-3 |
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123 | REAL(wp) :: devk53 = 0. |
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124 | REAL(wp) :: devk54 = 0.0794E-3 |
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125 | REAL(wp) :: devk55 = 0.3692E-3 |
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126 | |
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127 | !!---------------------------------------------------------------------- |
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128 | !! NEMO/TOP 3.3 , NEMO Consortium (2010) |
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129 | !! $Id$ |
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130 | !! Software governed by the CeCILL licence (NEMOGCM/NEMO_CeCILL.txt) |
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131 | !!---------------------------------------------------------------------- |
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132 | CONTAINS |
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133 | |
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134 | SUBROUTINE p4z_che |
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135 | !!--------------------------------------------------------------------- |
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136 | !! *** ROUTINE p4z_che *** |
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137 | !! |
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138 | !! ** Purpose : Sea water chemistry computed following OCMIP protocol |
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139 | !! |
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140 | !! ** Method : - ... |
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141 | !!--------------------------------------------------------------------- |
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142 | INTEGER :: ji, jj, jk |
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143 | REAL(wp) :: ztkel, zt , zt2 , zsal , zsal2 , zbuf1 , zbuf2 |
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144 | REAL(wp) :: ztgg , ztgg2, ztgg3 , ztgg4 , ztgg5 |
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145 | REAL(wp) :: zpres, ztc , zcl , zcpexp, zoxy , zcpexp2 |
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146 | REAL(wp) :: zsqrt, ztr , zlogt , zcek1 |
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147 | REAL(wp) :: zis , zis2 , zsal15, zisqrt |
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148 | REAL(wp) :: zckb , zck1 , zck2 , zckw , zak1 , zak2 , zakb , zaksp0, zakw |
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149 | REAL(wp) :: zst , zft , zcks , zckf , zaksp1 |
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150 | !!--------------------------------------------------------------------- |
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151 | ! |
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152 | IF( nn_timing == 1 ) CALL timing_start('p4z_che') |
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153 | ! |
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154 | ! CHEMICAL CONSTANTS - SURFACE LAYER |
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155 | ! ---------------------------------- |
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156 | DO jj = 1, jpj |
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157 | DO ji = 1, jpi |
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158 | ! ! SET ABSOLUTE TEMPERATURE |
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159 | ztkel = tsn(ji,jj,1,jp_tem) + 273.15 |
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160 | zt = ztkel * 0.01 |
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161 | zt2 = zt * zt |
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162 | zsal = tsn(ji,jj,1,jp_sal) + ( 1.- tmask(ji,jj,1) ) * 35. |
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163 | zsal2 = zsal * zsal |
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164 | zlogt = LOG( zt ) |
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165 | ! ! LN(K0) OF SOLUBILITY OF CO2 (EQ. 12, WEISS, 1980) |
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166 | ! ! AND FOR THE ATMOSPHERE FOR NON IDEAL GAS |
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167 | zcek1 = ca0 + ca1 / zt + ca2 * zlogt + ca3 * zt2 + zsal * ( ca4 + ca5 * zt + ca6 * zt2 ) |
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168 | ! ! SET SOLUBILITIES OF O2 AND CO2 |
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169 | chemc(ji,jj) = EXP( zcek1 ) * 1.e-6 * rhop(ji,jj,1) / 1000. ! mol/(L uatm) |
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170 | ! |
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171 | END DO |
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172 | END DO |
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173 | |
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174 | ! OXYGEN SOLUBILITY - DEEP OCEAN |
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175 | ! ------------------------------- |
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176 | DO jk = 1, jpk |
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177 | DO jj = 1, jpj |
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178 | DO ji = 1, jpi |
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179 | ztkel = tsn(ji,jj,jk,jp_tem) + 273.15 |
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180 | zsal = tsn(ji,jj,jk,jp_sal) + ( 1.- tmask(ji,jj,jk) ) * 35. |
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181 | zsal2 = zsal * zsal |
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182 | ztgg = LOG( ( 298.15 - tsn(ji,jj,jk,jp_tem) ) / ztkel ) ! Set the GORDON & GARCIA scaled temperature |
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183 | ztgg2 = ztgg * ztgg |
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184 | ztgg3 = ztgg2 * ztgg |
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185 | ztgg4 = ztgg3 * ztgg |
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186 | ztgg5 = ztgg4 * ztgg |
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187 | zoxy = ox0 + ox1 * ztgg + ox2 * ztgg2 + ox3 * ztgg3 + ox4 * ztgg4 + ox5 * ztgg5 & |
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188 | + zsal * ( ox6 + ox7 * ztgg + ox8 * ztgg2 + ox9 * ztgg3 ) + ox10 * zsal2 |
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189 | chemo2(ji,jj,jk) = ( EXP( zoxy ) * o2atm ) * oxyco * atcox ! mol/(L atm) |
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190 | END DO |
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191 | END DO |
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192 | END DO |
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193 | |
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194 | |
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195 | |
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196 | ! CHEMICAL CONSTANTS - DEEP OCEAN |
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197 | ! ------------------------------- |
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198 | DO jk = 1, jpk |
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199 | DO jj = 1, jpj |
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200 | DO ji = 1, jpi |
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201 | |
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202 | ! SET PRESSION |
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203 | zpres = 1.025e-1 * gdept_n(ji,jj,jk) |
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204 | |
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205 | ! SET ABSOLUTE TEMPERATURE |
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206 | ztkel = tsn(ji,jj,jk,jp_tem) + 273.15 |
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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(-4276.1 * ztr + 141.328 - 23.093 * zlogt & |
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228 | & + (-13856. * ztr + 324.57 - 47.986 * zlogt) * zisqrt & |
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229 | & + (35474. * ztr - 771.54 + 114.723 * zlogt) * zis & |
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230 | & - 2698. * ztr * zis**1.5 + 1776.* ztr * zis2 & |
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231 | & + LOG(1.0 - 0.001005 * zsal)) |
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232 | ! |
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233 | aphscale(ji,jj,jk) = ( 1. + zst / zcks ) |
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234 | |
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235 | ! DISSOCIATION CONSTANT FOR FLUORIDES on free H scale (Dickson and Riley 79) |
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236 | zckf = EXP( 1590.2*ztr - 12.641 + 1.525*zisqrt & |
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237 | & + LOG(1.0d0 - 0.001005d0*zsal) & |
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238 | & + LOG(1.0d0 + zst/zcks)) |
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239 | |
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240 | ! DISSOCIATION CONSTANT FOR CARBONATE AND BORATE |
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241 | zckb= (-8966.90 - 2890.53*zsqrt - 77.942*zsal & |
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242 | & + 1.728*zsal15 - 0.0996*zsal*zsal)*ztr & |
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243 | & + (148.0248 + 137.1942*zsqrt + 1.62142*zsal) & |
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244 | & + (-24.4344 - 25.085*zsqrt - 0.2474*zsal) & |
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245 | & * zlogt + 0.053105*zsqrt*ztkel |
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246 | |
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247 | |
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248 | zck1 = c10 * ztr + c11 + c12 * zlogt + c13 * zsal + c14 * zsal * zsal |
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249 | zck2 = c20 * ztr + c21 + c22 * zsal + c23 * zsal**2 |
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250 | |
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251 | ! PKW (H2O) (DICKSON AND RILEY, 1979) |
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252 | zckw = -13847.26*ztr + 148.9652 - 23.6521 * zlogt & |
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253 | & + (118.67*ztr - 5.977 + 1.0495 * zlogt) & |
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254 | & * zsqrt - 0.01615 * zsal |
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255 | |
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256 | ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE IN SEAWATER |
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257 | ! (S=27-43, T=2-25 DEG C) at pres =0 (atmos. pressure) (MUCCI 1983) |
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258 | zaksp0 = akcc1 + akcc2 * ztkel + akcc3 * ztr + akcc4 * LOG10( ztkel ) & |
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259 | & + ( akcc5 + akcc6 * ztkel + akcc7 * ztr ) * zsqrt + akcc8 * zsal + akcc9 * zsal15 |
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260 | |
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261 | ! K1, K2 OF CARBONIC ACID, KB OF BORIC ACID, KW (H2O) (LIT.?) |
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262 | zak1 = 10**(zck1) |
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263 | zak2 = 10**(zck2) |
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264 | zakb = EXP( zckb ) |
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265 | zakw = EXP( zckw ) |
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266 | zaksp1 = 10**(zaksp0) |
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267 | |
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268 | ! FORMULA FOR CPEXP AFTER EDMOND & GIESKES (1970) |
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269 | ! (REFERENCE TO CULBERSON & PYTKOQICZ (1968) AS MADE |
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270 | ! IN BROECKER ET AL. (1982) IS INCORRECT; HERE RGAS IS |
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271 | ! TAKEN TENFOLD TO CORRECT FOR THE NOTATION OF pres IN |
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272 | ! DBAR INSTEAD OF BAR AND THE EXPRESSION FOR CPEXP IS |
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273 | ! MULTIPLIED BY LN(10.) TO ALLOW USE OF EXP-FUNCTION |
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274 | ! WITH BASIS E IN THE FORMULA FOR AKSPP (CF. EDMOND |
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275 | ! & GIESKES (1970), P. 1285-1286 (THE SMALL |
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276 | ! FORMULA ON P. 1286 IS RIGHT AND CONSISTENT WITH THE |
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277 | ! SIGN IN PARTIAL MOLAR VOLUME CHANGE AS SHOWN ON P. 1285)) |
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278 | zcpexp = zpres /(rgas*ztkel) |
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279 | zcpexp2 = zpres * zpres/(rgas*ztkel) |
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280 | |
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281 | ! KB OF BORIC ACID, K1,K2 OF CARBONIC ACID PRESSURE |
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282 | ! CORRECTION AFTER CULBERSON AND PYTKOWICZ (1968) |
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283 | ! (CF. BROECKER ET AL., 1982) |
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284 | |
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285 | zbuf1 = - ( devk11 + devk21 * ztc + devk31 * ztc * ztc ) |
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286 | zbuf2 = 0.5 * ( devk41 + devk51 * ztc ) |
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287 | ak13(ji,jj,jk) = zak1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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288 | |
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289 | zbuf1 = - ( devk12 + devk22 * ztc + devk32 * ztc * ztc ) |
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290 | zbuf2 = 0.5 * ( devk42 + devk52 * ztc ) |
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291 | ak23(ji,jj,jk) = zak2 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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292 | |
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293 | zbuf1 = - ( devk13 + devk23 * ztc + devk33 * ztc * ztc ) |
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294 | zbuf2 = 0.5 * ( devk43 + devk53 * ztc ) |
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295 | akb3(ji,jj,jk) = zakb * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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296 | |
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297 | zbuf1 = - ( devk14 + devk24 * ztc + devk34 * ztc * ztc ) |
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298 | zbuf2 = 0.5 * ( devk44 + devk54 * ztc ) |
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299 | akw3(ji,jj,jk) = zakw * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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300 | |
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301 | |
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302 | ! APPARENT SOLUBILITY PRODUCT K'SP OF CALCITE |
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303 | ! AS FUNCTION OF PRESSURE FOLLOWING MILLERO |
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304 | ! (P. 1285) AND BERNER (1976) |
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305 | zbuf1 = - ( devk15 + devk25 * ztc + devk35 * ztc * ztc ) |
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306 | zbuf2 = 0.5 * ( devk45 + devk55 * ztc ) |
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307 | aksp(ji,jj,jk) = zaksp1 * EXP( zbuf1 * zcpexp + zbuf2 * zcpexp2 ) |
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308 | |
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309 | ! TOTAL BORATE CONCENTR. [MOLES/L] |
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310 | borat(ji,jj,jk) = bor1 * zcl * bor2 |
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311 | |
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312 | ! Iron and SIO3 saturation concentration from ... |
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313 | sio3eq(ji,jj,jk) = EXP( LOG( 10.) * ( 6.44 - 968. / ztkel ) ) * 1.e-6 |
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314 | fekeq (ji,jj,jk) = 10**( 17.27 - 1565.7 / ( 273.15 + ztc ) ) |
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315 | |
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316 | END DO |
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317 | END DO |
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318 | END DO |
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319 | ! |
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320 | IF( nn_timing == 1 ) CALL timing_stop('p4z_che') |
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321 | ! |
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322 | END SUBROUTINE p4z_che |
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323 | |
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324 | |
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325 | INTEGER FUNCTION p4z_che_alloc() |
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326 | !!---------------------------------------------------------------------- |
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327 | !! *** ROUTINE p4z_che_alloc *** |
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328 | !!---------------------------------------------------------------------- |
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329 | ALLOCATE( sio3eq(jpi,jpj,jpk), fekeq(jpi,jpj,jpk), chemc(jpi,jpj), chemo2(jpi,jpj,jpk), & |
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330 | & STAT=p4z_che_alloc ) |
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331 | ! |
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332 | IF( p4z_che_alloc /= 0 ) CALL ctl_warn('p4z_che_alloc : failed to allocate arrays.') |
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333 | ! |
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334 | END FUNCTION p4z_che_alloc |
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335 | |
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336 | #else |
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337 | !!====================================================================== |
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338 | !! Dummy module : No PISCES bio-model |
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339 | !!====================================================================== |
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340 | CONTAINS |
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341 | SUBROUTINE p4z_che( kt ) ! Empty routine |
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342 | INTEGER, INTENT(in) :: kt |
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343 | WRITE(*,*) 'p4z_che: You should not have seen this print! error?', kt |
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344 | END SUBROUTINE p4z_che |
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345 | #endif |
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346 | |
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347 | !!====================================================================== |
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348 | END MODULE p4zche |
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