Groundwater

Quality
Groundwater quality
• Groundwater quality refers to the state of water that is located
beneath Earth's surface.
 Groundwater can gather in
cracks in subsurface rocks and
in between soil particles.

The contamination of groundwater

can be serious, especially if the
water is a supply of drinking water
or water for crop irrigation.
Cont’d…
• The quality of groundwater is just as important as its
quantity.

• All groundwater contains salts in solution that are derived

from the location and past movement of the water.

• The quality required of a groundwater supply depends on

its purpose; thus, needs for drinking water, industrial water,
and irrigation water vary widely.
Cont’d…
• Groundwater tends to be less prone to contamination than
surface waters such as streams, rivers, and lakes because the
contaminants have to pass down through the ground to reach
the water.
Cont’d…
• Nevertheless, contamination can occur, especially if there
are cracks in overlying soil and rock through which the
toxic compounds can more easily flow.

• Since many compounds can dissolve in water and others

can be suspended in water, there is a potential for
contamination with toxic compounds.

• These include petroleum, hydrocarbons (oil), pesticides,

minerals, and disease-causing (pathogenic) microorganisms.
Cont’d…
• A list of the dissolved solids in any water is long, but it can
be divided into three groups: major constituents, minor
constituents, and trace elements (Table 1).

• The total mass of dissolved constituents is referred to as the

total dissolved solids (TDS) concentration.

• In water, all of the dissolved solids are either positively

charged ions (cations) or negatively charged ions (anions).
Cont’d…
• The groundwater in natural systems generally contains less

than 1000 mg/L dissolved solids, unless groundwater has:

(1) encountered a highly soluble minerals, such as gypsum

(2) been concentrated by evapotranspiration or

(3) been geothermally heated

Cont’d…
• The total negative charge of the anions always equals the
total positive charge of the cations.

• A higher TDS means that there are more cations and

anions in the water.

• With more ions in the water, the water’s electrical

conductivity (EC) increases
Units of Measurements
1. Common units are (1 mg/L = 1 ppm = 1000 ppb).
ppm = 1 part in 1,000,00 (106) parts by mass or volume

2. Molar concentration (molarity) = moles of solute per liter of solution.

molarity = moles of solute/ liter of solution

3. Molality = moles of solute per kilogram of solvent (not solution).

molality (M) = moles solute/kg of solvent

molality = (mg/l) *0.001/formula weight in grams

4. Equivalent weight of a substance is the amount of that substance

which supplies or consumes one mol of reactive species. An element's
equivalent weight is its atomic weight divided by its valence.
meq/l = (mg/l)/valence of ion
Units of Measurements
• In order to convert the mass concentration to an equivalent
concentration the following mathematical relationship is
used:
• (mass concentration) * (ionic charge) / (molecular weight)
= (equivalent concentration)

• For example, a water with a calcium concentration of 120

mg/L would have the following calcium equivalent
concentration:

• (120 mg/L) * (2 meq/mmol) / (40 mg/mmol) = (5 meq/L)

Example
• Tests for common ions are run on a sample of water and the

results are shown below. If a 10 percent error in the balance

is acceptable, shown the analysis be considered complete?

Constituents
• Ca2+= 55mg/L HCO3-= 250 mg/L
• Mg2+= 18 mg/L SO42-= 60 mg/L
• Na+= 98 mg/L Cl-= 89 mg/L
 Cont’d…
• Convert the concentrations of cations and anions from
milligrams per liter to milli equivalents per liter and sum
them.
Ion Cations Ion Anions
Conc, Equiv, Equiv Conc, Equiv, Equiv
Mg/L mg/meq Con, Mg/L mg/meq Con,
iv mg/L iv mg/L
Ca2+ 55 40/2 2.75 HCO3- 250 61/1 4.10

Mg2+ 18 24.3/2 1.48 SO42 60 96/2 1.25

Na+ 98 23/1 4.26 Cl- 89 35.5/1 2.51

Total 8.49 7.86

 Cont’d…
8.49−7.86
• Calculate percent of error: 𝑋100 = 8% < 10%
7.86

Therefore, accept analysis

Mequiv/L

0 2.75 4.23 8.49

Ca2+ Mg2+ Na+1

HCO3- SO42 Cl-

0 4.10 7.86
5.35
Mequiv/L
Graphical Interpretation of Water‐Quality Data
• Quality of water is determined by chemical analyses, the
data from which are used for various purposes, such as
classification, analysis, correlation, etc.

• For these purposes, the data need to be compiled and

statistically evaluated. Graphical and numerical
interpretation, a basic tool in hydrochemical studies, is
one of the means used for summarizing and presenting
water‐quality data.

• There exist a considerable number of methods and

procedures which can be applied.
What is a piper plot?
• A piper plot is a way of visualizing the chemistry of a
rock, soil, or water sample.

• It’s comprised of three pieces: a ternary diagram in the

lower left representing the cations, a ternary diagram in the
lower right representing the anions, and a diamond plot in
the middle representing a combination of the two.

• To plot, take the normalized concentrations of each of

your three cations for a sample and plot them on the lower
left ternary diagram, using the colored axes as guides.
Cont’d…
• Repeat for your anions on the lower right ternary diagram.
Now, following a line parallel to the outer axis of each
ternary diagram, project each point in the ternary diagrams
upward until they intersect with one another in the
diamond plot.

• This is where you draw the third point. These three points
represent one sample. Repeat for your other samples
Cont’d…
• A piper diagram is a graphical representation of
the chemistry of a water sample or samples.

• The cations and anions are shown by separate ternary plots.

The apexes of the cation plot
are calcium, magnesium and sodium plus potassium cations.

• The apexes of the anion plot

are sulfate, chloride and carbonate plus hydrogen
carbonate anions.

• The two ternary plots are then projected onto a diamond. The
diamond is a matrix transformation of a graph of the anions
(sulfate + chloride/ total anions) and cations
(sodium + potassium/total cations).
 Cont’d…
• The Piper diagram can be separated in hydrochemical
facies.
• Legend
• A: Calcium type;
• B: No dominant type;
• C: Magnesium type;
• D: Sodium and potassium type;
• E: Bicarbonate type;
• F: Sulphate type;
• G: Chloride type;
Cont’d…
• 1: Alkaline earths exceed alkalies;
• 2: Alkalies exceed alkaline earths;
• 3: Weak acids exceed strong acids;
• 4: Strong acids exceed weak acids;
• 5: Magnesium bicarbonate type;
• 6: Calcium chloride type;
• 7: Sodium chloride type;
• 8: Sodium bicarbonate type;
• 9: Mixed type
• Calculate %’s of each element on ternary diagram
• For example Ca is:

[Ca]
*100
[Ca] + [Mg] + [Na + K]
• Plot %’s on ternary diagrams
• Project each % onto diamond diagrams
 Stiff diagram
• A Stiff diagram, or Stiff pattern, is a graphical
representation of chemical analyses, first developed by
H.A. Stiff in 1951.

• It is widely used by hydrogeologists and geochemists to

display the major ion composition of a water sample.

• A polygonal shape is created from four parallel

horizontal axes extending on either side of a vertical
zero axis.
Cont’d…
• Cations are plotted in milliequivalents per liter on the left
side of the zero axis, one to each horizontal axis,
and anions are plotted on the right side.

• Stiff patterns are useful in making a rapid visual

comparison between water from different sources.

• An alternative to the Stiff diagram is the Maucha

diagram.
 Cont’d…
• Stiff diagrams can be used:
• 1) to help visualize ionically related waters from which a flow path can be
determined, or;
• 2) if the flow path is known, to show how the ionic composition of a water
body changes over space and/or time.

• Example of a Stiff diagram

• A typical Stiff diagram is shown in the figure (right). By standard
convention, Stiff diagrams are created by plotting the equivalent
concentration of the cations to the left of the center axis and anions to the
right. The points are connected to form the figure. When comparing Stiff
diagrams between different waters it is important to prepare each diagram
using the same ionic species, in the same order, on the same scale
Cont’d…
• Environmental laboratories typically report concentrations for
anion and cation parameters using units of mass/volume, usually
mg/L. In order to convert the mass concentration to an equivalent
concentration the following mathematical relationship is used:

• (mass concentration) * (ionic charge) / (molecular weight) =

(equivalent concentration)
• For example, a water with a calcium concentration of 120 mg/L
would have the following calcium equivalent concentration:

• (120 mg/L) * (2 meq/mmol) / (40 mg/mmol) = 6 meq/L