| solve_pH_from_AT {SolveSAPHE} | R Documentation |
Solver for the total alkalinity-pH equations
Description
Determines [H+] from Total alkalinity and dissolved total elements in sea water. Universal and robust algorithm from Munhoven (2013) with Newton- Raphson iterations
Usage
solve_pH_from_AT(p_alktot, p_dicvar, p_bortot, p_po4tot, p_siltot,
p_nh4tot, p_h2stot, p_so4tot, p_flutot, p_pHscale, p_dicsel,
p_askVal=FALSE, p_dissoc, p_temp=18, p_sal=35, p_pres=0, p_hini)Arguments
p_alktot |
Total alkalinity (mol/kg) |
p_dicvar |
Value of a carbonate system related variable : DIC, [CO2*], [HCO3-] or [CO3–] (mol/kg) See below parameter p_dicsel |
p_bortot |
Total boron concentration (mol/kg) |
p_po4tot |
Total phosphate concentration (mol/kg) |
p_siltot |
Total silicate concentration (mol/kg) |
p_nh4tot |
Total ammonia concentration (mol/kg) |
p_h2stot |
Total sulfide concentration (mol/kg) |
p_so4tot |
Total sulphate concentration (mol/kg) |
p_flutot |
Total fluor concentration (mol/kg) |
p_pHscale |
Chosen pH scale: "T" for the total scale, "F" for the free scale and "SWS" for using the seawater scale |
p_dicsel |
Carbonate variable selector (default = DIC). See parameter p_dicvar above. Values are: "DIC" : p_dicvar = DIC (Dissolved Inorganic Carbon) "CO2" : p_dicvar = [CO2*] "HCO3" : p_dicvar = [HCO3-] "CO3" : p_dicvar = [CO3–] |
p_askVal |
Optional boolean - set to TRUE if you want this function to return error on alkalinity, along with [H+] concentration value. Default is FALSE |
p_dissoc |
Named list of all dissociation constants. The list is optional but, if given, it should contain all members listed below excepted K2_Sil, which is itself optional. Member names are : K1_DIC : First dissociation constant of carbonic acid (mol/kg) on chosen scale K2_DIC : Second dissociation constant of carbonic acid (mol/kg) on chosen scale K_BT : Dissociation constant of boric acid (mol/kg) on chosen scale K1_PO4 : First dissociation constant of phosphoric acid (mol/kg) on chosen scale K2_PO4 : Second dissociation constant of phosphoric acid (mol/kg) on chosen scale K3_PO4 : third dissociation constant of phosphoric acid (mol/kg) on chosen scale K_Sil : First dissociation constant of sillicic acid (mol/kg) on chosen scale K2_Sil : Second dissociation constant of sillicic acid (mol/kg) on chosen scale. It is optional. If K2_Sil is absent from the list, then SiO2(OH)2 ion is not considered in the alkalinity equation. Only SiO(OH)3 ion is. K_NH4 : Dissociation constant of ammonium (mol/kg) on chosen scale K_H2S : Dissociation constant of hydrogen sulfide (mol/kg) on chosen scale K_HSO4 : Dissociation constant of hydrogen sulfate (mol/kg) on free scale K_HF : Dissociation constant of hydrogen fluoride (mol/kg) on free scale K_H2O : Dissociation constant of water (mol/kg) on chosen scale Note that all dissociation constants shall be expressed in chosen pH scale except K_HF and K_HSO4 which shall be in free scale. If the list is not given, these constants, excepted K2_Sil, will be calculated. |
p_temp |
Temperature in degree Celsius, to compute dissociation constants when p_dissoc is not given |
p_sal |
Salinity, in pratical salinty unit (psu), to compute dissociation constants when p_dissoc is not given |
p_pres |
Pressure, in bars, to compute dissociation constants when p_dissoc is not given |
p_hini |
Optional initial value of [H+] concentration If p_dicsel = "CO3", a vector of two initial values are expected since there may be two solutions for pH. Else, one initial value is expected |
Details
Formulations used when calculating dissociation constants:
Carbonate if Total pH scale: Luecker et al. (2000) – also Handbook (2007)
Carbonate if SWS or Free pH scale: Millero et al. (1995) – also Handbook (2007)
Boric acid: Dickson (1990, eq. 2 3) – also Handbook (2007, eq. 37)
Phosphoric acid: Yao and Millero (1995)
Silicic acid: Yao and Millero (1995) cited by Millero (1995)
Ammonium: Yao and Millero (1995)
Hydrogen sulfide: Millero et al. (1988) (cited by Millero (1995)
Hydrogen sulfate: Dickson (1990) – also Handbook (2007)
Fluoric acid if Total pH scale: Perez and Fraga (1987)
Fluoric acid if SWS or Free pH scale: Dickson and Riley (1979)
Water: Millero (1995)
This function does not support vectors as arguments, only scalar values.
Value
If p_dicsel is "CO3", there may be one or two solutions for [H+], else there is only one. In case there are two solutions, both are returned.
If you set p_askVal to TRUE, the function returns a data frame containing the following columns:
zh : [H+] concentration value(s) in the chosen pH scale
val : Error(s) on total alkalinity, that is the deviation between total alkalinity calculated from [H+] and given total alkalinity
If you set p_askVal to FALSE (default), the function returns only [H+] concentration value(s) in the chosen pH scale.
Author(s)
Guy Munhoven and Jean-Marie Epitalon
References
Munhoven G. Munhoven G. (2013) Mathematics of the total alkalinity-pH equation - pathway to robust and universal solution algorithms: the SolveSAPHE package v1.0.1. Geoscientif. Model Dev., 1367-1388
Examples
## Compute [H+] from Alkalinity total and DIC, on total pH scale
p_dissoc <- list()
p_dissoc$K1_DIC <- 1.421828e-06
p_dissoc$K2_DIC <- 1.081555e-09
p_dissoc$K_BT <- 2.526573e-09
p_dissoc$K1_PO4 <- 0.02408434
p_dissoc$K2_PO4 <- 1.076024e-06
p_dissoc$K3_PO4 <- 1.600484e-09
p_dissoc$K_Sil <- 4.071935e-10
p_dissoc$K_NH4 <- 5.380823e-10
p_dissoc$K_H2S <- 3.087264e-07
p_dissoc$K_HSO4 <- 0.1003021 # on free scale
p_dissoc$K_HF <- 0.00176441 # on free scale
p_dissoc$K_H2O <- 5.97496e-14
solve_pH_from_AT(p_alktot=2.5e-3, p_dicvar=2e-3, p_bortot=0.0004157, p_po4tot=0, p_siltot=0,
p_nh4tot=0, p_h2stot=0, p_so4tot=0.0282, p_flutot=6.832e-05, p_pHscale="T",
p_dicsel="DIC", p_dissoc=p_dissoc)
## Giving inital [H+] value and asking for final error on alkalinity, on seawater pH scale
result <- solve_pH_from_AT(p_alktot=0.00234, p_dicvar=0.001936461, p_bortot=0.0004157, p_po4tot=0,
p_siltot=0, p_nh4tot=0, p_h2stot=0, p_so4tot=0.0282, p_flutot=6.832e-05,
p_pHscale="SWS",p_dicsel="DIC", p_dissoc=p_dissoc, p_askVal=TRUE, p_hini=1.e-8)
H <- result$zh
error <- result$val
## Compute [H+] from Alkalinity total and CO3, on total free scale
H <- solve_pH_from_AT(p_alktot=0.00240, p_dicvar=2.775481e-04, p_bortot=0.0004157, p_po4tot=0,
p_siltot=0, p_nh4tot=0, p_h2stot=0, p_so4tot=0.0282, p_flutot=6.832e-05,
p_pHscale="F", p_dicsel="CO3", FALSE, p_dissoc=p_dissoc)
H1 <- H[1]
if (H[2] != 1) print ( c("Second solution : ", H[2]))