Species in natural freshwater

Central equilibriums in natural water samples KJM MEF 4010

Module 19

Compilation, calculations and QC of data

After the analysis the data must be: compiled reckoned in terms of

equivalent charge and

quality controlled by ion balance and agreement between measured and calculated conductivity

Statistical analysis

Correlation matrix Identify parameters

that are directly correlated or co-variate

Multivariate statistics How to interpret information in a data

matrix of 1000 samples with typically 20 – 30 parameters

Cluster analysis

Organizing parameters that co-variate in clusters Identify

• Links between parameters and groups of parameters

• Identify key explanatory factors

• General patterns

NO3-K+Cl-

Na+HCO3

Mg2+

Ca2+

Free P

O4SO

42-

DOCSAR

sUVa

H+

25,00

50,00

75,00

100,00

Variables

Sim

ilari

ty

DendrogramComplete Linkage; Correlation Coefficient Distance

DNOM Geology Agriculture Seasalts

Principal Component Analysis Makes an n-dimential graph of your

n parameters Identifies the greatest variation in the swarm of data

points and draws the PC1 through its axis.

Identifies the next PC perpendicular to the previous

Produce loading plots that are projections of the points to the PC plane 0,40,30,20,10,0-0,1-0,2-0,3

0,2

0,1

0,0

-0,1

-0,2

-0,3

-0,4

-0,5

First Component

Seco

nd C

ompo

nent

HCO3

Free PO4

Cl-

NO3-

SO42-

K+Na+

Mg2+

Ca2+

DOCSAR

sUVa

H+

Loading Plot of H+; ...; HCO3

Acid Alkaline

Organic

Inorganic

45,3%

29,3

%

43210-1-2-3

3

2

1

0

-1

-2

First Component

Seco

nd C

ompo

nent

Nesøytjernet

Kolbotnvann

Årungen

Gjersjøen

Østensjøvannet

Lutvann

Sværsvann

Akerselva

Maridalsvannet

Score Plot of H+; ...; DOP

Dystrophic

Soft dilute

Hard alkaline

Eutrophic

0

500

1000

1500

2000

2500

3000

ueq/

L

Org. charge PO43- Tot-F Cl- NO3- SO42- HCO3- H+ K+ Na+ Mg2+ Ca2+

Challenges with simultaneous equilibrium

Speciation programs (MINEQL)

Inorganic complexes

Major cations in natural waters H+, Ca2+, Mg2+, Na+, K+

Common ligands in natural systems: HCO3

-, SO42-, NO3

-, Cl-, F- & organic anions In anoxic environment: HS- & S2-

Dominating species in aerobic freshwater at pH 8 are:

Metal ion Dominating species % Mn+aq of

total amount of M

Mg(II) Mg(H2O)62+ 94

Ca(II) Ca(H2O)62+ 94

Al(III) Al(OH)2(H2O)4+, Al(OH)3(H2O)3

0, Al(OH)4(H2O)2- 1•10-7

Mn(IV) MnO2(H2O)20 -

Fe(III) Fe(OH)2(H2O)4+, Fe(OH)3(H2O)3

0, Fe(OH)4(H2O)2- 2•10-9

Ni(II) Ni(H2O)62+, NiCO3(H2O)5

0 40 Cu(II) CuCO3(H2O)2

0, Cu(OH)2(H2O)20 1

Zn(II) Zn(H2O)42+, ZnCO3(H2O)2

0 40 Pb(II) PbCO3(H2O)4

0 5

Hydrolysis

85.22 H4Al(OH)OH4Al

25.17 H3Al(OH)OH3Al

55.10 H2Al(OH)OH2Al

954 H Al(OH) OH Al

6.5 HAl(OH)OHAl(OH)

75.6 HAl(OH)OHAl(OH)

6.5 HAl(OH)OHAl(OH)

954 HAl(OH)OHAl

43214aq

42aq3

3213aq 0

32aq3

212aq22aq3

11aq2

2aq3

4aq42aq0

3

3aq0

32aq2

2aq22aq2

1aq2

2aq3

=+++=+↔+

=++=+↔+

=+=+↔+

==+↔+

=+↔+

=+↔+

=+↔+

=+↔+

+−+

++

+++

+++

+−

++

+++

+++

pKpKpKpKp

pKpKpKp

pKpKp

.pKp

pK

pK

pK

.pK

β

β

β

β

In aqueous systems, hydrolysis reactions are important Hydrolysis reactions are controlled by {H+}

• The higher the pH, the stronger the hydrolysis of metal cations

• E.g. Aluminium

• Al3+aq denotes Al(H2O)6

3+

Distribution of dissolved Fe3+ species Two total Fe concentrations, FeT = 10-4M and FeT = 10-2M

FeT = 10-4 M

%Fe

0

20

40

60

80

100

FeT = 10-2 M

pH1 2 3 4

%Fe

0

20

40

60

80

100

Fe3+

FeOH2+

Fe(OH)2+

Fe2(OH)24+

Fe3+

FeOH2+

Fe(OH)2+

8

10

12

14

160 2 4 6 8 10 12 14

pHp

X

pFe

pFe(OH)

pFe(OH)2

pFe(OH)3

pFe(OH)4

Distribution diagrams

Dissolved Organic Matter Low molecular weight (LMW)

< 1000Da (e.g. C32H80O33N5P0.3) E.g.:

High molecular weight 1000 - > 100 000Da Humic substance

• Very complex and coloured substances

Measured by

TOC/DOC Or by

UV absorbency or colour

Speciation with different ligands present In aqueous solution, containing a number of metal cations and

ligand anions, there are several simultaneous equilibriums Important ligands in natural water systems

• Basic: CO32-, OH-, Org-, Cl-

• Acid: F-, SO42-, Org-, Cl-

The distribution of species will depend on factors such as ligand concentrations, temperature, pH and ionic strength

The calculations become very complex where a metal cation have the opportunity to bind to more than one type of ligands Multiple iterations of the calculations are necessary

For such calculations we apply computer programs as MINEQL+, ALCHEMI or PHREEQ-C

E.g. simple system with only Al3+ and F-

Relevant balanced equilibrium reactions

Definition of unknown

Equilibrium expressions Mass balance

Charge balance

No of unknown <

No of equations

Solve equations

Are assumptions justified?

No

Yes

No

Yes

Scheme for chemical equilibrium calculations

1 2 and 3

Approximations are commonly done by assuming the concentration of specific species are 0 Molar

Only mass balance and charge balance equations can be simplified

Approximations

New Approximations

Set of expressions 1. Equilibrium expressions

– KW, KSP, KA, KB, βn, KREDOX, Kd

2. Mass (read: concentration) balance – Set the equilibrium molarities (MX)

up against each other (MX vs. MY) and against the analytical molarity (MX vs. cX) – Analytical concentration is the concentration of a substance dumped

into a solution. It includes all the forms of that substance in the solution.

3. Charge balance – Σ eqv./L positive charge = Σ eqv./L negative charge

1. Equilibrium expressions • KW, KSP, KA, KB, βn, KREDOX, Kd

K H O OHW = + −[ ][ ]3

K Ba SOSP = + −[ ][ ]2

4

2

K H O CH COOCH COOHA =

+ −[ ][ ][ ]3 3

3

K OH CH COOHCH COOB =−

−

[ ][ ][ ]

3

3βn

n

n

n

Ni CNNi CN

=−

+ −

[ ( ) ][ ][ ]

2

2

K Mn FeMnO Fe HdOksRe

[ ][ ][ ][ ] [ ]

=+ +

− + +

2 3 5

4

2 5 8K

IId

org

aq

=[ ][ ]

2

2

2. Mass balance • Ex.1: BaSO4 in HCl solution

– We see from the molecular formula that: So that:

The hydroniumion (H+) has two sources:

HCl (=cHCL) and the auto-proteolysis of water (=[OH¯]):

• Ex.2: Ag2CrO4 solution – We see from the molecular formula that : So that :

3. Charge balance • The law of physics demand that

– Number of positive charge is equal to number of negative charge Charge contribution of a specie

= Valens · Molar concentration

Ex. 1: – In neutral pH solutions one can disregard the H+ and OH- ions

Ex. 2: – No new information

Σ Σn X m Yn m⋅ = ⋅+ −[ ] [ ]

Metal hydrolysis The hydrolysis is described by a set of equilibrium reactions

{Fe3+} is determined by replacing each of the other parts of the mass equation with their equilibrium expression expressed by {Fe3+} :

Then the other species can be determined from the {Fe3+} and β E.g.;

}{Fe(OH)}{Fe(OH)}Fe(OH){}{Fe(OH)}{Fe

7.22 H4Fe(OH)OH4Fe

8.13 H3Fe(OH)OH3Fe

31.6 H2Fe(OH)OH2Fe

05.3 H Fe(OH) OH Fe

4

032

23

43214aq

42aq3

3213aq 0

32aq3

212aq22aq3

11aq2

2aq3

−+++

+−+

++

+++

+++

++++=

=+++=+↔+

=++=+↔+

=+=+↔+

==+↔+

C

pKpKpKpKp

pKpKpKp

pKpKp

pKp

β

β

β

β

2

32

2 }{}{)( +

++ =

HFeOHFe β

2

32

2

3

22

2

aq22aq3

}H{}{Fe}{Fe(OH)

}{Fe}H{}{Fe(OH)

H2Fe(OH)OH2Fe

+

++

+

++

+++

=

•=

+↔+

β

β

++++= ++++

+4

43

32

213

}{H}{H}{H}{H1}{Fe ββββC

Speciation programmes MINEQL+ is a chemical

equilibrium model capable of calculating aqueous speciation solid phase saturation precipitation-dissolution adsorption.

An extensive thermodynamic database is included in the model

Speciation; Shortcomings The equilibrium model is based on a choice of

complexes and their stability constants, which makes the results questionable

Tutorial

Start out by choosing components that define your system

Find thermodynamic constants in database in ”Scan Thermo”

Tutorial

The Calculation Wizards Tool is a collection of 5 input options to describe the chemistry of the system

Running the

calculation

Tutorial Multirun manager

Titration 2 way analysis Field data

Output manager Types of Output

• The Header • The Log • The MultiRun Table • Component Groups • Special Reports

Tutorial

Graphics manager Bar and X-Y plots

Run through the 4 problems

Report

The report (~ 3p) should include the following paragraphs Abstract Introduction Material and methods Results Discussion Conclusion