A Computer Program for a Trilinear Diagram Plot
and Analysis of Water Mixing Systems
by Michael D. Morris, Jeffrey A. Berk,
Joseph W. Krul
ABSTRACT
‘The Piper (1953) trilinear diagram has been widely
used to graphically represent the dissolved constituents of
natural waters and to test for apparent mixtures of waters
from different sources. Because of the time required to plot
points and calculate the proportional values of mixing, this
treatment of data was often quite tedious, particulaely in
studies involving large numbers of chemical analyses. The
PIPER program was written in BASIC to be ran on @
Hewlett-Packard desktop computer with an X-¥ plotter.
Data input isin ppm units. The program plots points in all
three fields ofthe trilinear diagram, draws at each point
within the central diamond field a circle with 2 radius
correspondent to the concentrations exprested in meq/l,
checks for points that fall on a straight line (or within «
predetermined tolerance of a straight line) representing
postulated mixtures with two end members, and/or within
a triangle representing mixtures of three end members
Finally, the program does a numerical analysis of the
‘mixing ratios of the constituents for postulated mixing
systems according to the methodology as presented by
Piper (1953),
“Department of Geology, Kent State University
Contribution No. 241
Department of Geology, Kent State University,
Kent, Ohio 44242,
Received April 1982, revised August 1982, accepced
September 1982.
Discussion open until July 1, 1983
Vol. 21, No. 1-GROUND WATER—January-February 1983
INTRODUCTION
In a graphical treatment of chemical analyses
of ground water developed by Piper (1953), the
character of a ground water can be expressed by
three points located in three different fields. The
points represent: (1) percentage-reacting equiva-
lents of three major cation constituents (Mg"", Na"
and Ca’*) in a cation triangular field ; (2) percent-
age-reacting equivalents of three major anion
constituents (CI, SO; and HCO3) in an anion
triangular field; and (3) the point in the diamond-
shaped field representing the overall chemical
character of the solution. The last point is plotted
at the intersection of rays projected from the
points in the anion and cation triangular fields into
the diamond field (Figure 1).
Piper's graphical treatment of the chemical
analysis allows for an easy discrimination of
distinct water types by their plottings in various
subareas of the diamond field (Figure 2). Piper
(1953) also suggested that water analysis repre-
sented by points aligning along a straight line in
all three fields should be tested for the possibility
that they represent a part of a mixing system. A
solution produced by a mixture of two end
members is represented in each of the three fields
as.a point which is located on a straight line in
between the points representing the two end
members. Moreover, the individual ionic constitu-
ents in the mixture will all have been mixed in the
same proportions. Similarly, in the case of a
mixture from three sources, the solution will be
67Fig. 1. Piper's (1953) tril
represented in each of the three fields by a point
located inside a triangle defined by the three
end members, Again, all the ionic constituents will
have been mixed in the same proportions.
When only a few points are plotted on a tri-
linear diagram, it is rather easy to discern and con-
firm a binary mixing by “eyeballing” of three
points aligned on a straight line in all three fields
and to make the appropriate computations (Piper,
1953). To discern and confirm a ternary mixing
system is more complex. When the number of
chemical analyses involved is large, the task of
YW)
Fig. 2, Water types on a trilinear diagram:
area 1 — (Ca"? + Mg") > (Na’ + K");
area 2 — (Ca"? + Mg") <(Na" + K*);
area 3 — (HCO5 +03") > (er +803);
92 4 — (HCO; + COs") < (cI + S04);
125 — carbonate hardness (secondary alkalinity) > 60%:
12 6 — noncarbonate hardnoss (secondary salinity) > 50%:
22 7 — noncarbonate alkali (primary salinity) > 50%;
228 — carbonate alkali (primary alkalinity) > 50%;
12 9 — no dominant eation-anion pair.
singling out all possible mixing systems and testing
each for validity is extremely tedious, as well as
is the mere task of production of a trilinear
diagram for a large number of analyses. The follow-
ing computer program is designed to plot up to
100 chemical analyses on a trilinear diagram and
then scan simultaneously all the analyses, testing
for all the possible combinations in binary and
ternary mixing systems,
‘The program was designed to place points in
all three fields and to calculate and test the pro-
portions needed to postulate possible mixing
relationships. Although this program produces
reliable calculations for a wide variety of chemical
compositions, the user is cautioned that the
results can be significantly affected by the selec-
tion of input values and certain user-specified
options. The user is further cautioned that
interpretations must reflect the specific field
conditions and locations from which the water
samples were collected.
Our computer program is based on Piper's
(1953) original assumptions
1, All of the major constituents have been
included in the calculations,
2. All ions are assumed to remain in solution,
3. All the Fe, Al, and Si are present in the
water in a colloidal state as oxides and are not in
chemical equilibrium with the ionized constituents,
‘Therefore, these elements are not included in
calculations of total concentration,
4. Minor constituents of ground water are
summed with the six major constituents to which.
they are respectively related in chemical properties.
5, Water consisting of substantial quantities
of free acid cannot be fully represented on the
diagram
‘The program was written in Hewlett-Packard
enhanced BASIC for use on a HP 9845A desktop
computer with an optional 9872B X-Y plotter.
Options within the program allow graphics to be
produced on the cathode-ray-tube (CRT) display,
the thermal printer, or the X-Y plotter. Minor
variations should allow this program to be adapted
to other computers using BASIC, Due to memory
limitations on the HP 9845A, the program is
actually subdivided into two smaller routines
linked together. “PIPER,” the first portion of the
program, is used to input and store data, compute
unit conversions and to plot the resulting percent-
age values on the trilinear diagram. The mixingcalculations may then be performed by the second
portion of the program named “MIXING.” The
transfer of control to the second routine is accom-
plished in line 3680 of “PIPER” utilizing the LINK
command in order to conserve all variables defined
earlier, Depending on the computer capabilities
that the program is going to be adapted to, it may
be stored as one long program or several smaller
routines. A flow diagram of the program is shown
in Figure 3,
Fig, 3. Flow chart of “PIPER” and “MIXING.”
INPUT OF RAW DATA
Input concentrations of various constituents
must be in units of parts per million (ppm). The
program will convert these units to meq/l, and
further to percentage of total dissolved solids.
‘The program asks for the six major constitu-
cents: (Ca"*, Mg’, Na’, CI, SO’ and HCO) and
only K", CO3 and NO} as second-rank constitu-
ents, Other second-rank constituents can be added
with only minor changes in the program. In a
single run of the program, data from a maximum,
of 100 sources may be entered, stored, plotted and
tested for mixing trends.
Data input can come from keyboard or data
previously stored on a data file. Creation of a data
file after input from the keyboard is a user’s option.
PLOTTING AND COMPUTATIONAL
PROCEDURES
‘The plotting of points and the drawing of the
outline of the triangles and diamond both are done
in cartesian coordinates on the H-P graphics system.
All trilinear coordinates must be converted to X-Y
coordinates. The units used are millimeters for the
CRT and will vary on the X-Y plotter depending
on the size of the plot. The plotting field is 184.47
by 149.82 units. The primary trilinear diagram is
an equilateral triangle with sides divided into 100
units. For ease in reading, cation and anion sub-
triangles are offset from the upper diamond. The
subtriangles are equilateral with sides of 50 units
representing a range of 0 to 100% of a specified
constituent.
‘The height of a triangle (Figure 4) is calcu-
lated in the following manner:
Fig. 4. Dimensional ri
trilinear diagram,
atan 60° = AY/(50/2)
AY = 25(tan 60°)
AY = 43.30 units
In similar fashion, the dimensions of the
diamond field are found to be 50 units wide and
86.60 units in height.
Points within the cation triangle, if plotted by
hhand, are based on the percentage-reacting values
of Ca’?, Mg"?, Na’ and K°; if plotted by this
program, the points (Figure 5) are based on the
percentage of Ca’? and Mg”? compared to the total
cations, Points within the anion triangle are calcu-
lated and plotted in a similar fashion based on the
percentages of SO? and HCO3. The relevant
equations are as follows:
Fig. 5. Coordinate system in the triangular fields of a
‘eilinear diagram,
y Mg? (%6) y" SOF (%6)
25(tan 60°) 100 25 (tan 60°) 100
100 ¥" = 25 tan 60° Mg’? (%) 100 Y" = 25 tan 60° SO;*0%)
an 69° ME?) van 69" S02 0%)
4
tan 60° = Y'/X" tan 60° = Y"/X"
X' = Y/tan 60° X" = Y"/tan 60°
Recalling the conversion: 2% ion concentration = 1 unit on the plotting field
9 (99) EBB ys X,, = Xp HCOs (66) LEME
“a 2% LAR 3 2%
Ca’? (%) Yy" HCO} (%) Y"
Xq=Xq - Be
is a 2 tan 60° = 2 tan 60°
Keg = Xpy — £42) _ tan 60" Mg 04 _ HCO3(%) _ tan 60° SOF (4/4
ee tan 60° 7 2 tan 60°
Ca‘? (%) _— Mg*? (9%). HCO; (%) SO? (%)
Xx = Xgi- Xi =Xpo
as eee + ee 4
Yq 2¥q+¥" Yp+¥"
Mg"? (%6) Oz (%6)
Yq = Yo + tan 60° Y, = Ya + tan 60°
4
The location of points in the diamond is at the intersection of rays projected from points in the anion
and cation triangles. In the computer program it is calculated and plotted based on the reacting percentages
of HCO; and (Na") + (K*) (Figure 6).
To plot the point in the diamond field as shown in Figure 6, the following equations were derived:
Xp’ > Xp
00 units
Lunit
2%
Xz - Xp’ = (Nat + K"(%)
anLunit
Xp’ Xy = HCO} (%)
2%
(Xp ~ Xp) = (Ny ~ Xp) = 4 [OX — Xp) (Kye — Ky) ~ (Ny — Xp]
HCO (%) _(Na’ + K")(06)
Xp — Xs) = 50-
Oer~ Xs) 4 +
Xp = Xp! + (Xp — Xp!) = (Xpt~ Xy) ~ (Kp > Xs)
Xp + 100-HE ay 10 Eco eoeins SKI)
X= Xp + 50 HCO , (Nal + VC
+ +
% TS] = 60°
-¥.
tan 60° =_1—1
Xr~ Xs
Yy - Yy = tan 60° (Xy - Xs)
HCO} (%) _ (Nat + KD)
4 4 1
= tan 60° [50~
_tan 60°
[200 ~ HCO} (9%) ~ (Na” + K")(%6)}
= 86.60 — 4330 [HCO5 (%) + (Na’ + K*)(%)]
Yy = Yq" + 86.60 ~ 4330 [HCO (%) + (Na’ + K°)(%5)]
Analyses may be plotted with a point, an symbols, There has not been a provision for over-
identification number, or by choice of five other prints.
Piper proposed using citcles, whose areas are
proportional to the absolute concentrations of the
sources, plotted around points in the central
diamond field. Our program plots circles whose
radii are based on the sum of meqj/l and are propor-
tionally represented with cither an arithmetic scale
at a user-defined proportion or a logarithmic scale.
DETERMINATION OF MIXING BETWEEN
‘TWO END MEMBERS
Primary criterion for ground-water mixing is
that the flow directions must physically bring
waters from two sources together. This criterion
cannot be judged by the computer program and
must not be overlooked by the operator. The
second criterion for determination of a binary
mixing system is based on the assumption that
when two waters mix in any proportion and all
products remain in solution, the mixture will plot
somewhere on a straight line between the two end
Fig. 6. Coordinate system in the diamond field ofa trilinear members in all three fields of the trilinear diagram.
diagram. ‘The total concentration for the mixture in thediamond field must be intermediate between the
total concentration of the two end members,
whereas the concentration of the mixture (the
absolute concentration and the concentration of
the specific constituents) must all be in equal
proportionate volumes (Figure 7; Piper, 1953). Our
‘computer program analyzes all the elements of this
criterion and either confirms or disproves apparent
mixtures.
One of the most important decisions required
from the user of this program is to determine the
acceptable tolerance away from a straight line
for a group of any three points being considered
as a possible mixing combination. A user-specified
Fig. 7. Binary mixing system in the diamond field of the
trilinear
afb = (Vp X E9)/(Vq X Ea)
ValMy = (bX Eq i/la Ey)
Em = [Ey X Ep X (a+ BI /LlaX Eq) + (6X Ep)
Va (bX Ep)/lla X Ey) + (bX Eg]
Vy = (aX Egi/lla X E4) + (bX Ey)
Cry = (Cy X Va) + (Cy X Vo)
— distances measured on the diagram;
= concentrations of respective waters having
compositions A, B and M:
Vr, = proportionate volume in mixture M of water
having composition
Vp = proportionate volume in mixture M of water
having composition B;
Cm = calculated concentration of the mixture M.
2
tolerance away from a true straight line is incorpo-
rated, Based on an acceptable analytical error, a
five percent tolerance is normally used. Deviation
allowed away from a straight line is a function of
the length of that line and the user-specified
tolerance. Possible mixing points must fit inside a
tolerance window. If a point falls more than the
preset percentage away from the straight line, the
tested combination of three points is rejected as
not a mixing system. For example, when 2 five
percent tolerance has been specified, a mixing
point on a line seven units long would be con-
sidered if the point was within .35 units off the
line. In clusters of points (ie., very short lines)
even very small analytical errors would cause mix-
tures to be disqualified, All points representing a
postulated mixing system may deviate from theit
plotted positions. The maximum amount they may
deviate is assumed to be the same as the user-de-
fined percent tolerance. If both end points in a
binary mixing system have maximum variance in
opposing directions, the line is either lengthened or
shortened. The length of the line is compared to
the maximum possible variation. If that amount of
possible variance is greater than the length of the
line, the program considers these points a cluster.
‘The allowed tolerance away from the cluster of
points, representing similar percentage of reacting
concentrations, is equal to the user-specified
percentage
To test for possible mixtures, all points are
considered in all combinations of pairs as end
members, and the remaining points are tested to
see if they fit within a “tolerance window” around
the line, The limits of the window are the maxi-
mum plus the tolerance, and the minimum minus
the tolerance for both the X and Y values of the
end points (Figure 8), The window is further
limited within two parallel lines on either side of,
and at the specified tolerance away from the line
under consideration,
‘The user should be cautioned that the mixing
systems identified by the computer program con-
form with the mathematical criteria only (Piper,
1953).
THREE-WAY MIXING
Piper also suggested a method to check for a
ternary mixture resulting from three end members,
‘This technique treats the three end-member com:
positions, when plotted, as apexes of a hypo-
thetical triangle in each plotting field. The first
criterion for a hypothetical mixture point for the
program to consider is that it must plot within theTBE erin
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75APPENDIX I. PROGRAM LISTING*
TRUE Fore
* Copies of the program may be obrained on disc
(single, or double density) or tape-cassette for a nominal
fee by contacting Dr. Yoram Eckstein, Department of
Geology, Kent State University, Kent, Ohio +4242,
74