The Concept of Alkalinity Alkalinity is one of the most central but perhaps not the best understood concept

in aquatic chemistry.1 As a novice one is confronted with several different types of alkalinity (e.g. M, P, and caustic alkalinity), as well as several different definitions of alkalinity (chemical, experimental, physical, mathematical). Advantages of the alkalinity concept are:

it is a conservative quantity which remains unaffected by changes in temperature, pressure or pH it is easily experimentally accessible (by titration with strong acids until an endpoint) it is a measure of waters ability to resist pH changes (due to addition of st rong acids and bases) Addition or remove of weak acids or bases does not change the alkalinity. Experimental definition: The alkalinity of a solution is its Acid Neutralizing Capacity (ANC) when the endpoint of the titration is the CO2 (or H2CO3*) equivalence point, which is typically at pH 4.2 4.5: (1) alkalinity = ANC to 4.2 4.5 In addition, the following terms are used interchangeably for alkalinity (all are the same or have the same numerical value): (2) alkalinity = total alkalinity TAlk = M alkalinity = Carbonate Hardness CH

Mathematical Definition: Main Idea Let us consider a NaCl-CO2-H2O system. Electroneutrality dictates: (3) [Na+] [Cl-] [HCO3-] 2 [CO3-2] + [H+] [OH-] = 0

Put all ions on the left that do not change their amount of protons when titrated to pH 4.3 4.5, and all other ions on the right-hand-side: (4) [Na+] [Cl-] = [HCO3-] + 2 [CO3-2] [H+] + [OH-]

The left-hand side is a constant. Thus, the right-hand side must also be a constant. The constant on the right-hand side is called alkalinity, more precisely, total alkalinity (TAlk): (5) alkalinity = TAlk = [HCO3-] + 2 [CO3-2] [H+] + [OH-]

This is the definition which is valid for most natural waters. It comprises the three main ions (HCO3-, CO3-2, and OH-) that consume protons H+. In addition, hydrochemistry programs such as PhreeqC and aqion consider also all the other species that consum protons.

The General Case The physical definition of alkalinity (based on the principle of electroneutrality) is the charge difference between conservative cations and anions: (6) alkalinity = TAlk = conservative cations conservative anions

Conservative ions are ions that remain unaffected by changes of pH: Na+, K+, Ca+2, Mg+2, Cl-, SO4-2, NO3- and others. According to Eq.(6), total alkalinity is expressed as (7) TAlk = [Na+] + [K+] + 2 [Ca+2] + 2 [Mg+2+ + [Cl-] 2 [SO4-2] [NO3-]

This more general approach to calculate alkalinity is used in PhreeqC and aqion. In aqionalkalinity is used as input as output to calculate DIC and complete carbonate speciation for any aqueous solution

Units of Alkalinity Alkalinity is expressed in units of eq/L or meq/L (which is the same as val/L or mval/L) which is the modern and more fundamental choice (favored by aqion). In practice, however, the use of ppm CaCO3 is also preferred. A conversion chart is given here. References 1 Morel, F.M.M. and J.G. Hering: Principles and Applications of Aquatic Chemistry (2nd ed.), John Wiley, New York, 1993 M Alkalinity and P Alkalinity Types of Alkalinity Alkalinities are classified acording to the endpoint of the titration with acid: (1a) (1b) (1c) M Alkalinity = Alkalinity = Total Alkalinity P Alkalinity = Carbonate Alkalinity Caustic Alkalinity (endpoint: CO2 equivalence point) (endpoint: HCO3- equivalence point) (endpoint: CO3-2 equivalence point)

Here, M refers to the pH indicator methyl orange (endpoint of about 4.2 to 4.5); P refers to the pH indicator phenolphtalein (endpoint of about 8.2 to 8.3). Please note that M alkalinity is what we usually define as alkalinity or total alkalinity. *The equivalence points (enpoints of titration) are not fixed quantities; they vary as shown in thisexample.] For a simple carbonate system alkalinities are defined by proton balance (mole balance for H+) which yields:

(2a) (2b) (2c)

M Alkalinity P Alkalinity Caustic Alkalinity

= ( [OH-] [H+] ) + [HCO3-] + 2 [CO3-2] = ( [OH-] [H+] ) + [CO3-2] [H2CO3*] = ( [OH-] [H+] ) [HCO3-] 2 [H2CO3*]

Substracting M alkalinity from P alkalinity yields the total amount of dissolved inorganic carbon: (3) M P = [H2CO3*] + [HCO3-] + [CO3-2] = DIC

where H2CO3* symbolizes the composite carbonic acid. Note: The above equations are only valid when the solution does not contain any weakacid or base. In contrast, aqion calculates the M and P alkalinity starting from the general concept of alkalinity. The calculated values are outputted here and here. Approximate Alkalinity Relationships We consider the pH range above the M alkalinity endpoint, i.e. pH > 4.2. In this range, the species H2CO3* and H+ can be neglected, and Eqs.(2a) and (2b) simplify to: (4a) (4b) M Alkalinity P Alkalinity [OH-] + [HCO3-] + 2 [CO3-2] [OH-] + [CO3-2]

Let us now consider five special cases which we obtain after inserting the following five conditions into Eqs.(4a) and (4b): (5) (6) (7) (8) (9) [OH-] = 0 [OH-] = 0 [OH-] = 0 [HCO3-] = 0 [HCO3-] = 0 , [CO3-2] = 0 , [HCO3-] = 0 , [CO3-2] = 0 [HCO3-] = M [HCO3-] = M 2P [CO3-2] = M/2 [CO3-2] = M P [OH-] = M and and and and and P=0 P = [CO3-2] P = [CO3-2] [OH-] = 2P M P=M

These results can be rearranged into the following table where Eq.(5) corresponds to column P=0, Eq.(6) to column P<M/2, Eq.(7) to column P=M/2, Eq.(8) to column P>M/2, and Eq.(9) to column P=M: - P=0 [OH-] 2 [CO3-2] P < M/2 P = M/2 P > M/2 P=M

- 0 0 0 2P 0 M 2P-M 2(M-P) M 0

[HCO3-] [OH-] + 2 [CO3-2] + [HCO3-]

M-2P

- M M M M M

- The bottom raw represents the sum of each column. According to Eq.(4a) the sum of the first column embodies the M alkalinity. This equality is fulfilled across the whole table. The above table is often used in (older) literature by water treatment profesionals to estimate the content of bicarbonate and carbonate in the solution from measured M and P alkalinities. However, using hydrochemical models such like PhreeqC or aqion the concentration of HCO3- and CO3-2 are calculated directly and with high precision based on thermodynamic data (so there is no need for the above approximations). Two remarks are necessary: 1. In the above equations and table, [HCO3-] represents the free bicarbonate HCO3- plus all bicarbonate complexes such as CaHCO3+. Similarly, [CO3-2] represents the freecarbonate CO32 plus all carbonate complexes such as CaCO3. 2. The quantities in square brackets are given in molar units such as mol/L or mmol/L. Thus, the quantity 2 *CO3-2+ in the first column of the table stands for carbonate in eq/L or meq/L (which is the same as val/L or mval/L). Three Equivalence Points (EP) In the simple carbonate system we consider three equivalence points (EP) which are the pH values of the following three solutions:

The pH value (equivalence point) depends on the total carbonate concentration C T, i.e. the DIC. In addition it also depends (on lesser degree) on the ionic strenght. The diagram below shows the equivalence points of the carbonate system as a function of DIC. The three curves were calculated with aqion in 13 logarithmic steps from 10-12 to 101 M DIC (an example calculation for 10-3 M is presented here).

With increasing DIC also the ionic strength increases. [Please note that the largest value of 10 M DIC corresponding to the most upper points in the diagram already exceeds the applicability range of aqion.] Natural waters are usually in the DIC range of 1 to 10 mM, i.e. 10-3 to 10-2 M. In particular, at 1 mM we have the equivalence points (taken from here): Finally, the three equivalence points play an important role in the concept of ANC andalkalinity:

Electrical Conductivity (EC) Calculation Methods The electrical conductivity (EC) or specific conductance is a useful water-quality parameter. There are several methods available to calucalate EC.1 Three of them are used by the program: Linear approach (proportional to ionic strength) Nonlinear approach (Inverse Marion-Babcock) Approach based on diffusion coefficients (Appelo 2010)2 default method The approach can be selected in Settings in the upper menu bar. The first two approaches are simple empirical methods based on the ionic strength. The third approach is based on diffusion coefficients; it is the default method of aqion. The calculated value of EC is displayed in the output tables in units of S/cm. Both values are shown: EC at the given temperature T and EC25 at 25C after temperature compensation. Conversion of Units The physical units of EC take a little getting used to. The conversions between S/cm (micro Siemens per centimeter) and other EC units are:

1 mS/m 1 dS/m 1 dS/m 1 mho/cm

= = = =

10 S/cm 1000 S/cm 1 mS/cm 1 S/cm

where 1 S = 1 Siemens = 1 ohm-1 = 1 mho. The program uses S/cm as default. Typical Conductivities of Aqueous Solutions absolute pure water destilled water rain water potable water groundwater industrial wastewater seawater concentrated acids and bases 0.055 0.5 5 30 500 1000 30 2000 5000 54 000 up to 1 000 000
+ -

S/cm S/cm S/cm S/cm S/cm S/cm S/cm S/cm

Pure Water. Due to the self ionization of water into H und OH ions, the electrical conductivity of absolute pure water is non-zero: EC = 0.055 S/cm at 25C. Temperature Compensation The EC of most natural waters, including seawater, increases with temperature 1-3% per degree Celsius. Measured EC values are usually referred to 25C often indicated by EC25. For this purpose the program converts the calculated EC (valid for the given water temperature T) to EC25 at 25C: (1) EC_25 EC (T) EC25 = EC / [ 1 + a (T - 25) ] when checkbox Mol is activated when checkbox Mol is deactivated

with a = 0.019 C-1 and T in C. Both values are displayed in the output tables:

[It is sometimes instructive to switch between EC and EC25 in order to get a feeling for the not-so-small temperature effect.] Linear Approach based on Ionic Strength The simplest empirical method is based on a linear relationship between electrical conductivity and ionic strength I: (2) EC (S/cm) = 6.2 104 I (mol/L)

This is equivalent to the common approximation (i.e. the inverse of Eq.(1)): (3) I (mol/L) = 1.6 10-5 EC (S/cm)

The ionic strength I that enters Eq.(2) is determined by the actual water composition/speciation as: (4) I=12iz2ici where the sum runs over all ions i with concentration ci and charge number zi. Note that, in contrast to this exact formula for I, the formula for EC in Eq.(2) is only approximate. TDS. There is also a simple linear relationship between EC value and TDS see here. Nonlinear Approach (Inverse Marion-Babcock) The nonlinear approach is based on the ionic strength, too. According to Sposito3, who adopts the results of Marion & Babcock4, the relationship between EC and I is given by (5) log10 I = 1.159 + 1.009 log10 EC for I 0.3 mol/L In this equation the units of I are mmol/L (= mM) and the units of EC are dS/m which differ essentially from the units in Eq.(2). The rearrangement of Eq.(5) into a form similar to Eq.(2) can be done as follows: log10 (EC / dSm-1) log10 (10-3 EC / Scm-1) log10 (EC / Scm-1) - 3 log10 (EC / Scm-1) This yields (6) EC (S/cm) = 6.67 104 [ I (mol/L) ] 0.991 = = = = 0.991 log10 (I / mM) - 1.149 0.991 log10 (103 I/M) - 1.149 0.991 [ 3 + log10 (I/M) ] - 1.149 4.824 + log10 (I/M)

1.

2. 3. 4.

Because I0.991 I, this equation is very similar to Eq.(2). Thus, this approach can be also called pseudo-linear. Due to a slightly larger prefactor in Eq.(6), however, the EC of the nonlinear approach slightly exceeds the EC of the linear approach. *The name inverse Marion-Babcock results from the fact that we rearranged the original equation from I to EC.] References R.B. McCleskey, D.K. Nordstrom, and J.N. Ryan: Comparison of electrical conductivity calculation methods for natural waters, Limnol. Oceanogr.: Methods 10, 952967 (2012) C.A.J. Appelo: Specific conductance how to calculate, to use, and the pitfalls (2010), http://www.xs4all.nl/~appt/exmpls/sc.html Garrison Sposito: The Chemistry of Soils, 2nd Edition, Oxford University Press, 2008, (see Eq.(4.23) p.111) G.M. Marion, K.L. Babcock: Predicting specific conductance and salt concentration in dilute aqueous solutions. Soil Sci. 122, 181187 (1976)

TDS - Total Dissolved Solids TDS is a measure of all dissolved substances in water that can pass through a very small filter (a sieve measuring 2 m). aqion calculates TDS as the sum of all ions: 1 (1) TDS = cations + anions The calculated TDS value is displayed in in the output table in units of mg/L (or ppm). Since TDS is made up of inorganic salts it is often referred to salinity. The three so-called sum parameters (TDS, EC, and ionic strength) depend on all ions dissolved in the aqueous solution and are related to each other. For example, TDS and EC are related by the empirical linear relationship: where the conversion factor ranges between 0.55 and 0.70. On the other hand, a simple rule of thumb is:

Another empirical formula relates ionic strength I with TDS: Last but not least, TDS is a helpful parameter to check the correctness of a water sample.
1

Organic compounds and suspended particles are ignored here.

TDS, EC, and Charge Balance TDS (or EC ) together with the charge balance error CBE are useful parameters to check the correctness of a water sample. Both, TDS and CBE are in some sense complementary: Instead of TDS one can also use the electrical conductivity (EC) because they are (approximately) proportional to each other: aqion calculates all three parameters: CBE, EC, and TDS. Now compare the measured EC with the calculated EC (or the measured TDS with the calculated), and you get helpful information about the water sample:

CBE negative EC measured > EC calculated EC measured < EC calculated deficiency of cations surplus of anions

CBE positive deficiency of anions surplus of cations

Exactly the same holds if LF is replaced by TDS in the table.

What is the optimal parameter for charge-balance adjustment? The above table helps to select the optimal parameter (cation or anion) for chargebalance adjustment. In principal, the following cations and anions are available: 1 In this way, the above table can be converted into the following recommendation for the parameter selection: CBE negative EC measured > EC calculated EC measured < EC calculated Ca, Mg, Na, K, Fe, Al, Mn, NH4+ DIC, Cl, Sulfate, Nitrate CBE positive DIC, Cl, Sulfate, Nitrate Ca, Mg, Na, K, Fe, Al, Mn, NH4+

What happens if I act against this recommendation, i.e. if I select a cation/anion whilst an anion/cation is proposed? Well, in such a case the discrepancy between the measured and calculated EC (or TDS) will increase. The above considerations are implemented into aqion in form of an interactive Guidancefor charge-balance adjustment.
1

The parameter list contains only these elements that are de facto present in the actual input water (with a minimum concentration of 1 mol/L). For example, if the input water does not contain any Al, then Al is absent in the parameter list.

Water Hardness Total Hardness TH Total hardness is a measure of the total concentrations of Ca and Mg ions in water (i.e. the main alkaline-earth metals1): (1) Total Hardness TH = [Ca] + [Mg] There are several water hardness scales in use. For example, it can be expressed in meq/L (SI units), or in ppm CaCO3, or in German hardness dH: (2) (3) (4) TH in meq/L TH in ppm TH in dH = = = 2 ( [Ca in mM] + [Mg in mM] ) 100.1 ( [Ca in mM] + [Mg in mM] ) 0.1339 [Ca in mg/L] + 0.2307 [Mg in mg/L]

Conversation rules to other units are given in the table below. Temporary and Permanent Hardness

The above Eq.(1) divides the total hardness into the two major cations, Ca and Mg. Another way is to divide the total hardness according its anionic content into carbonate hardness CH (temporary hardness) and non-carbonate hardness NCH (permanent hardness): (5) Total Hardness TH = CH + NCH Carbonate hardness is directly related to alkalinity: (6) (7) CH in meq/L CH in dH = = [Alk in meq/L] 2.809 [Alk in meq/L]

aqion calculates both TH und CH which is displayed here. The non-carbonate hardness is then the difference of both quantities: (8) NCH = TH CH

Carbonate hardness is named temporary hardness because Ca and Mg carbonates precipitate as minerals upon heating, whereas Ca and Mg associated with sulfates, chlorides, or nitrates do not precipitate upon heating (therefore NCH = permanent hardness). The Special Case TH < CH According to Eq.(6) the carbonate hardness CH seems redundant and could be replaced by the parameter alkalinity throughout. However, there are cases where the relation CH = Alk does not work. Consider, for example, a pure H2CO3 solution that does not contain any Ca or Mg. Due to Eq.(1) the total hardness is zero, despite the presence of alkalinity which would suggest a non-zero CH (and a negative NCH). To avoid this paradox, such cases are treated as follows: (9) when TH < CH , then CH = TH und NCH = 0

This rule is meaningful for CH as temporary hardness because carbonates can precipitate only if Ca and/or Mg are present. In the above example there are no Ca and Mg, and, hence, there is no precipitation, i.e. CH = TH = 0 (irrespective of the fact that Alk > 0). Computational Algorithm The algorithm to compute TH and CH is simple and consists of three steps in aqion: step 1 step 2 step 3 TH = [Ca] + [Mg] CH = [Alk] when TH < CH , then CH = TH

All calculations are performed in units of mM or meq/L. Only afterwards the hardness is transformed into ppm CaCO3 (English program version) or into dH (German program version). The total hardness TH is used to classify aqueous solutions into four hardness categories. Conversion Chart Hardness is expressed in different units (which vary from country to country):

(10) (11) (12) (13)

German Degrees: French Degrees: English Degrees: 1 ppm CaCO3 (US norm) :

1 dH 1 fH 1 e 1 a

= = = =

10 mg/L CaO 10 mg/L CaCO3 10 mg CaCO3 in 0.7 L 1 mg/L CaCO3 2

These definitions are interrelated by simple conversion rules:

ppm CaCO3 1 ppm CaCO3 1 dH 1 fH 1 e 1 meq/L 1 mM 1 17.8 10.0 14.3 50.04 100.09

dH 0.06 1 0.56 0.80 2.8 5.6

fH 0.10 1.78 1 1.43 5 10

e 0.07 1.25 0.70 1 3.51 7.02

meq/L 0.02 0.357 0.2 0.285 1 2

mM 0.01 0.178 0.1 0.142 0.5 1

The conversion factors in this table follow directly from the molar weights of calcium carbonate and calcium oxide: (14) (15) CaCO3: CaO: 100.09 g/mol 56.08 g/mol or or 1 mg/L CaCO3 10 mg/L CaO = = 0.010 mM 0.178 mM

Other alkaline-earth metals like strontium and barium have no significant contribution to TH because they are found in trace amounts in natural waters. 2 ppm (parts per milion) is defined als 1 ppm = 1 mg / 1 kg = 10-6. For diluted solutions with density 1 kg/L the numerical value of both concentration units, ppm and mg/L, are equal. Soft and Hard Water The U.S. Geological Survey uses the following classification into hard and soft water (based on Total Hardness TH): Water Type soft moderately hard TH in ppm CaCO3 < 60 60 to 120 TH in dH < 3.35 3.35 to 6.7 TH in mM < 0.6 0.6 to 1.2 TH in meq/L < 1.2 1.2 to 2.4

hard very hard

120 to 180 > 180

6.7 to 10.05 > 10.05

1.2 to 1.8 > 1.8

2.4 to 3.6 > 3.6

Just this scheme is used by aqionto classify aqueous solutions into four water types. One example of amoderately hard water is shown in the right screen shot.