GROUND WATER ANALYSIS FOR SELECTED IONS OF
 
TYPICAL WELLS IN THE EMPORIA, KANSAS V"ICINITY
 
A Thesis
 
Presented to
 
the Department of Chemistry
 
Kansas State Teachers Col lege of Emporia
 
In Partial Fulfi I Iment 
of the Requirements for the Degree 
Master of Science in Chemistry 
by 
David A. Holdeman
 
June, 1971
 
"TS09TC
 
t
 
•.c' ,""" / I . L­
ACKNOWLEDGMENTS 
The author is indebted to Dr. A. T. Ericson for his assistance 
and encouragement and to the other members of his committee. 
Acknowledgment and appreciation are also expressed to his wife 
who was understanding and helpful while this study was in progress. 
TABLE OF CONTENTS 
CHAPTER PAGE 
I. INTRODUCTION •••••...•...• 
I I. EXPERIMENTAL PREPARATION AND ANALYSIS 3 
Preparation of Solutions . . . 4 
Procedure • • . . • • • 
. . 7 
II I. DATA AND DATA ANALYSIS. 
. . . . . . 17 
IV. DISCUSSION .••••• 30 
BIBLIOGRAPHY ••••••••• , 
. . . 32 
LIST OF TABLES 
TABLE	 PAGE 
1. Standardization of AgN03 Solution Using Low Concentration 
Ch lor tde. • • • • • • • • • • . • • • • • • • • • • • •• 10
 
2. Turbidimetric Sulfate Cal ibration Curve Data • . . • . • .. 14
 
3. Data from Wei Is Located Upstream from Emporia. • . • • • •• 19
 
4. Data from WeI Is Located Downstream from Emporia. . • . . .. 20
 
5. Water Hardness Data from Wei Is Located Upstream from Emporia 21
 
6. Water Hardness Data from Wei Is Located Downstream from 
Emporia .•..•••. • • • • • • . . . . • • • . • •. 22
 
7. Hard Water Data from Wei Is Located Upstream from Emporia •. 23
 
8. Water Hardness Data from Wei Is Located Downstream from Emporia 24
 
9.	 Precipitation in the Emporia Area from January 28, through
 
March 31, 1971.. • • • • • • • • • • . • • . . . . • • •• 25
 
LI ST OF FIGURES 
FIGURE PAGE 
1• Curve for the Titration of 25. ml 0.100 F Na2C03 with 
0.100 N Hel .•••..•.•....•.•..••• ., 9
 
2. Calibration Curve for Determination of Sulfate Ion. • • 16 
3. We I I Locat ions • • • • • • • • • • • • • • • • • • • • • •• 18
 
4. Concentration of Ca+2 vs. Concentration of HC03- • 29
 
CHAPTER I 
INTRODUCTION 
Ground water' In the Emporia vicinity was analyzed to determine 
the minerai content found in the water. The analysis was carried out 
to determine the acidity, the ionic concentration by conductance, the 
water temperature, and the calcium ion, magnesium ion, bicarbonate ion, 
chloride ion, and sulfate ion concentrations. These ions are aqueous 
constituents of ground water found in this area. 
Emphasis was placed upon the development of the method for deter­
 mination of the sulfate lon, because there is no accepted accurate 
method for its determination. 
The water used In the analysis was obtained by periodic sampl ing 
of selected wei Is outside of the Emporia city limits. The sampl ings 
were made from untreated taps which were used for domestic purposes or 
for livestock watering. The tests for water temperature and acidity 
were made at the sampling location using a thermometer and a portable 
pH meter. The remainder of the analysis was done in the Kansas State 
Teachers Col lege c~emistry laboratories. 
Ground water Is the water below the surface of the land that 
supplies water to wei Is and springs. The origin of the water which 
becomes ground water is prlmari Iy precipitation or seepage from streams.' 
The amount of mineral content found In such water is dependent on the 
source of the water and the medium through which it is flowing. The water 
retains any soluble Ion which it has dissolved or has been dumped Into it. 
2 
Emporia is located between the Cottonwood and Neosho Rivers. The 
areai geology points out that Emporia is located almost entirely on 
terrace gravel and alluvium deposited by the two rivers. A prel iminary
 ' 
,investigation was initiated to determine if the ground water found in 
cross-sections of the terrain on the upriver and downriver sides would 
yield any decrease or increase of the major common mineral content. The 
data obtained wi I I determine the presence of permanent and temporary 
hardness, and indicate varying ionic concentrations at each location 
sampled over a two month period. This investigation represents the only 
recent ground water analysis data for this area. The methods for analysis 
of the ions determined In this study are outlined to provide easy, rapid, 
and relatively accurate procedures for primary ground water analysis. 
CHAPTER II 
EXPERIMENTAL PREPARATION AND ANALYSIS 
There are many different opinions of what method to use in the 
analysis of water. Each method is the result of studies made on different 
types of water found In various areas. AI I of the methods have some 
importance In studying the type of waters which the methods were devel­
 oped to analyze. The various methods lack specific ion accuracy because 
there are ion simi larities. AI I of the methods used in this study are 
outl ined in the book Standard Methods i£c the Examination £i Water, Sewage, 
~ Industrial Wastes. This book is the source of the procedures pre­
 sently fol lowed by the Kansas Water and Sewage Laboratory. Some of the 
analytical procedures employed In this investigation are revisions of 
these standard procedures. 
As an insight to the probable I imits of the concentration of the 
ions to be determined, a I iterature search was made to find any avai lable 
material. The literature avai lable on ground water in Lyon County is 
very limited. The only publ ished information about Lyon County ground 
water which is known to the University of Kansas Publication Director, 
Mr. Diaz of the U. S. Geological Survey, and Mr. Stoltenberg of the Water 
and Sewage Laboratory of the Kansas State Board of Health, is but a 
single publ ication, "Geology, Mineral Resources, and Ground Water Resources 
of Lyon County, Kansas" Part ~ by Howard G. O'Connor (1953). The analysis 
in this study was only a single sampl ing of some thirty-three wei Is in 
the entire county. The laboratory work was done by the state laboratories. 
In the study, only two of the wei Is sampled were located in the vicinity 
of the wei I sites In this study. 
4 
Preparation of Solutions 
The solutions for these analyses were prepared from reagent grade 
chemicals. The burettes used In the titration analyses were three-way 
Teflon stopcock, class A, Kimax microburettes and straight Teflon stop­
 cock, class A, Kimax microburettes. 
Conductance Analysis 
The only prepared solution used in this analysis is a standard 
0.100 N KCI solution which was prepared by adding 0.7456 grams of Baker 
Reagent Grade Potassium Chloride to make one I iter of solution. 
~ Analysis 
The standard base used in this analysis was prepared from Mal I in­
 ckrodt Sodium Hydroxide. Due to the fact that sodium hydroxide sol id 
absorbs water rapidly, the solution was prepared by weighing approxi­
 mately 8 grams of the solid and pouring that into a two I iter volumetric 
flask. Deionized water was then added to the mark. Smal I samples of 
dried Mal I inckrodt Primary Standard Potassium Biphthalate were weighed 
and solvated with 50 ml deionized water and then titrated with the pre­
 pared sodium hydroxide to a phenolphthalein endpoint. 
The hydrochloric acid used In the analysis was prepared by pipet­
 tlng 16.6 ml of concentrated Mal I Inckrodt Hydrochloric Acid into a I iter 
of water and then dl luting to two liters. To standardize the acid, a 
5.00 ml al iquot was taken and titrated with standard NaOH to a phenolphthalein 
endpoint. 
The Indicator, phenolphthalein was prepared by dissolving 1 g sol id 
phenolphthalein In 100 ml 60% ethyl alcohol. 
5
 
The indicator, bromocresol green, was prepared by dissolving 0.10 g
 
solid bromocresol green in 100 ml 20% ethyl alcohol.
 
Chloride Analysis 
The reagent for this analysis was 0.10 N si Iver nitrate. It was 
prepared from dried Reagent Grade Si Iver Nitrate. A liter of solution 
was prepared from 16.991 grams of the dried sol ide The solution was 
standardized using smal I dissolved samples of dried Baker & Adamson 
. Reagent Grade Sod i urn Ch lor ide. 
The indicator used In the analysis Is the absorption indicator, 
dichlorofluorescein. It was prepared by dissolving 0.10 g of dichloro­
 fluorescein in 100 ml 70% ethyl alcohol. 
Calcium-Magnesium Analysis 
The reagents used In sample preparation were concentrated nitric 
acid, methyl red indicator and 2.5 M sodium hydroxide. 
The nitric acid was Reagent Grade Baker &Adamson stock. 
The 2.5 M sod fum hydroxIde was prepared by dissolving 10.0 grams 
of sodium hydroxide pel lets in water to a volume of 100 mi. 
The methyl red indicator was prepared by dissolving .1 g methyl 
red Indicator into 250 ml 60% ethyl alcohol. 
The titration reagents were composed of 0.1 disodium ethylene­
 diaminetetraacetlc acid (Na2EDTA), a pH 10 buffer, .1 MMgS04 and Eriochrome 
Black T indicator. 
The Na2EDTA was prepared by weighing 37.255 grams of the sol id 
into a I iter volumetric flask and di luting to the mark. 
The magnesium sulfate was prepared by weighing 11.960 grams of 
dried Mal Ilnckrodt Analytical Reagent Magnesium Sulfate into a liter 
6 
vOlumetric flask and diluting to the mark. This was then standardized 
using the Na2EDTA solution. 
The pH 10 buffer was prepared by di luting 570. ml of Mal I inckrodt 
Analytical Reagent Grade Ammonium Hydroxide (sp. gr. 0.90) and 70. g of 
Mal Iinckrodt Analytical Reagent Grade Ammonium Chloride to a liter with 
deionized water. 
The Eriochrome Black T indicator was prepared by dissolving 0.10 
grams of Matheson, Coleman &Bell Eriochrome Black T in 25 ml of Mal I inckrodt 
Analytical Reagent Grade Methanol. 
Sulfate Analysis 
The solutions necessary for the sulfate analysis were standard 
sodium sulfate, 1 M barium chloride and the conditioner. 
The standard sulfate solution was prepared from Matheson, Coleman 
&Bel I Reagent Grade Sodium Sulfate. The solution was made to a concen­
 tration of 113 ppm by adding 0.1673 grams of dried Na2S04 to a I Iter 
volumetric flask and di luting with deionized water. 
The BaC'2 solution was prepared by adding 66.0 grams of Mal linckrodt 
Analytical Reagent Grade Barium Chloride, dihydrate, into a 250 ml volu­
 metric flask and diluting with deionized water. 
The conditioner was prepared by first dissolving 25 ml Mal I inckrodt 
Glycerine In 50 ml Mal linckrodt N. F. Isopropyl Alcohol. This was fol lowed 
by addition of 150 ml deionized water and 38 grams of Baker &Adamson 
Reagent Grade Sodium Chloride. The final additive was 15 ml of Mal I in­
 ckrodt Reagent Grade Hydrochloric Acid. 
7
 
Procedure 
Sampling Preparation 
After setting general sampl ing locations, the next aspect of the 
project entai led the cleaning of an appropriate number of two I iter glass 
bottles. Each bottle was first washed with soap solution and rinsed in 
tap water. This was fol lowed by adding a coating of nitric acid and 
sodium dichromate cleaning solution. These were rinsed in tap water and 
then about fifty mi Iii liters of one molar disodlum ehtylenediamine­
 tetraacetic acid was rinsed through each bottle to remove any complexable 
metals present. Finally, the bottles were rinsed several times with 
deionized water and al lowed to dry overnight. 
Sampling Procedure 
All of the samples were taken from an untreated faucet at or near 
the wei I proper. At the time of sampl ing, the wei Is were either being 
used or if not several gal Ions of water was discharged before the sample 
bottle was fi I led. The thermometer was rinsed and a test tube of water 
was taken for pH determination after the bottle fi I led. 
Determination of Water Temperature 
. "7il?tBl::'J\Hef "'1't" U.Z....'% ••·n,wr.:lI!rttl.i:'·:tiie·4r:.......···ff.ner.$c:tbrn1i,f:Jc,e.Jrtla I 
.."..•"LI;~f~j~h~,iI11omef~fwagt1hmers~8 6rf' Tocaf Tgn . 
Determination of mi 
At the sampl ing site, the Orion Research lonalyzer Specific Ion 
Meter Model 404 was adjusted using the standard buffer. The Sargent Com­
 binatlon Calomel-Glass Electrode was then Inserted into the test tube and 
the pH read directly from the meter. 
8 
The remainder of the water analyses was carried out in the
 
laboratory.
 
Determination of Conductance 
Conductivity measures the abi I ity of a material to conduct an 
electrical current. The conductivity of water is proportional to the 
concentration of the cations and anions present and the temperature of 
the sample. Conductivity values were obtained by first calculating a 
cel I constant using a solution of known conductivity. The resistance 
-of this solution was measured and the celi constant calculated from 
the fol lowing relationship: 
cel I constant = conductivity x resistance 
. A standard solution of 0.10 molar potassium chloride was used as the 
known. It had a defined conductivity of 1412 micromhos. The experi­
 mentat resistance was determined to be 725 ohms. The calculated cel I 
constant was 1.24. 
The instrument used in the analyses was an Industrial Instrument
 
Type RC Conductivity Bridge. The conductivity cel I contained a pair of
 
platinum discs coated with platinum black. The discs were 1.2 cm in
 
diameter and 3.0 cm apart.
 
The determination was made by pouring a 150 ml al iquot of sample 
in a 180 ml tal I form beaker. The cel I was rinsed several times with 
deionized water and air dried. The cel I was then submerged in the sample 
and the reading was taken as experimental conductance. The conductivity 
of the water samples is equal to the cel I constant C times the experimental 
conductance Cx. 
Conductivity = C x Cx 
9
 
An estimate of the mi I I lequivalent concentration of anions or cations can 
be made by multiplying the conductance by 0.01. 1,7 
Determination of Carbonate-Bicarbonate 
Since much of the rock in the area is I imestone, it appears logical 
that there would be an appreciable amount of carbonate and bicarbonate 
found In the water. The pH of the water samples was found to range from 
6.6 to 7.3. The titration curve of sodium carbonate with hydrochloric 
acid (Figure 1),3 indicates that carbonate ion Is essentially non-existant 
at these pH values. 
12 I i 
10 
8 
== 6 ~ 
4 
o I I I I I , j 
o 10 20 30 40 50 60 
Volume 0.100 N HCI (ml) 
FIGURE 1 
CURVE FOR THE TITRATION OF 2.5 ML 0.100 F Na2C03 WITH 0.100 N HCL 
Bicarbonate that would be present at the observed pH was determined 
by the titration of a 50 ml al iquot of the water sample with 0.100 N HCI. 
The acid was added to a bromocresol green endpoint. The solution was then 
bol led to remove dissolved carbon dioxide and then the Titration was 
completed. 3 
10 
Determination of Chloride 
Two possible sources of chloride ion are sodium chloride deposits 
and calcium chloride from underground deposits or as a salt for melting 
Ice and snow.' There are two generally used methods for chloride deter­
 mlnatlon. They consist of the gravimetric and vOlumetric precipitation 
techniques. Both employ si Iver Ion as precipitation agent and in this 
investigation it appeared reasonable to use the faster vOlumetric method. 
There are several variations of the volumetric technique. The endpoint 
may be determined with Indicators, by conductivity changes or by potential 
changes with suitable Indicator electrodes. The use of this method 
neglected the interference from bromide and iodide that may have been 
present In smal I quantities. Previous work indicates that these ions 
are found in negl igible amounts. 1 
The analysis was of a 50 ml al iquot of sample. To the sample 
was added 3 drops of dichloroflouresceln Indicator. The silver nitrate 
solution was added with vigorous stirring. About 1 percent before the 
endpoint, flocculation occurred. The titration continued unti I the 
precipitate obtained a I ight pink color. 4 
The concentration range of this technique was reported to be 0.025 
N to 0.005 N,3 but from the subsequent data it appears that the procedure 
was useable down to about 0.002 N. 3 
TABLE 
STANDARDIZATION OF AgN03 SOLUTION USING LOW CONCENTRATION CHLORIDE 
Sample of NaCI Norma I ity Volume of Norma I ity 
in 50 ml H2O of NaCI A9 N03 of AgN03 
0.020569 0.0070 3.45 ml 0.0994 N 
0.00945g 0.0032 1.62 mI 0.0998 N 
0.00592g 0.0020 1.00 mI 0.1010 N 
11 
This data does not however go to the lowest level in which it is felt that 
the method wi II detect. At the lowest concentration titrated for standard­
 ization of the si Iver nitrate, the endpoint was wei 1· defined. These values 
are relatively accurate considering the standardization using highor con­
 centrations yielded a value of 0.1008 N for the standard si Iver nitrate 
solution. 
Determination of Ca+2 and Mg±2 
The most commonly used technique for the determination of calcium 
and magnesium is that of compleximetric titration with ethylenediamine­
 tetraacetic acid. A compleximetric titration of calcium and magnesium 
can be completed in about five minutes. The disadvantage of the method 
is that many other metal ions also complex and interfere with the analysis. 
Iron would probably be the only significant interference in the data to 
fol low. Ca and Mg complex most readily at a pH of over 10, for this 
reason it Is necessary to maintain this pH continually. This is pro­
 vided for by the ammonia buffer. This technique was developed for deter­
 mination of hard water. The 50 ml aliquot sample is acidified with one 
or two drops of concentrated nitric acid and boi led. This is done to 
prevent the precipitation of calcium carbonate. 7 The cool solution is 
then neutral ized with NaOH to a methyl red endpoint. The combined calcium 
and magnesium concentration is determined by taking this sample and adding 
2 ml of the ammonia buffer and 3 drops of Eriochrome Black T indicator and 
titrating with disodium ethylenediaminetetraacetic acid (Na2EDTA). The 
color change is from red to blue for this titration. This is because 
reaction of the metal with the indicator. 
Mln- + H+ ~ Hln-2 + M+2 
red blue 
12 
M is the metal and In-3 is the indicator. With the Na2EDTA competing with 
the Indicator for the metal, the color change appears only at the point 
where essentially al I of the metal Ion has been complexed with the Na ZEDTA. 3 
The calcium determination was made by back titration of the above 
solution. The solution is taken and back titrated to a red color with 
3
 standard M9So4• It should be noted that if the magnesium present is 
sma I I in relation to the calcium present, the method for magnesium is 
somewhat uncertain. 7 
Determination of Sulfate 
At present, there are few rapid methods for determination of sul­
 fate. There are even fewer techniques which provide reproduceabJe, 
accurate data. For this reason several different methods for determina­
 tlon were attempted unsuccessfully. They ranged from the precipitation 
by barium chloride with back titration with EDTA to the direct titration 
with barium chloride using the indicator tetrahydroxyquinone (THQ). These 
techniques ental I many step procedures or misleading endpoints. It was 
finally decided to do the determination by turbidimetry. This technique 
is a fast, direct method for the sulfate determination. The sulfate ion 
is precipitated with barium ion in acid solution in such a manner as to 
form barium sulfate crystals of uniform size. Light is then passed 
through the solution and the amount of light blocked off by the precipitate 
is proportional to the concentration of the sulfate ion present in the 
solution. For the particle size to be uniform, there must be uniform 
mixing of the solution and the rate of addition of barium chloride must 
remain constant. It is known that an acid solution wll I al low relatively 
uniform particles growth, but the problem was to find a suitable solution 
that when added would also keep the particles In suspension to stab; I ize 
13 
readings. The solution used was a mixture of hydrochloric acid, sodium 
chloride, isopropyl alcohol, glycerine, and water. It was cal led the 
conditloner. 2 
The method for making the cal ibration curve fol lowed a standard· 
procedure. A 50 ml aliquot of sample was to be used for the unknown 
samples. To make the· curve, 2 ml, 4 ml, 6 ml, 8 ml, 10 ml, 12 ml, and 
14 ml of standard sulfate solution was mixed with the required remainder 
of deionized water to obtain a 50 ml al iquot. At the time of use, the 
solution was mixed with 10 ml of the conditioner and set on the constant 
rate magnetic stirrer. After agitating for several seconds, two ml of 
1 M barium chloride wa~ added rapidly via a 50 ml burette. At the instant 
of addition, the timer was started. The solution was stirred for one 
minute and then set aside to al low for particle growth. Four minutes 
after stirring, the solution was introduced into a Coleman 14 cuvette 
and inserted into the sample side of the cuvette carriage. The blank 
compartment of the carriage contained a ~uvette containing a blank solu­
 tion made of 50.0 ml deionized water, 10.0 ml conditioner, and 2.0 ml 
of 1 M barium chloride. The sample carriage was then inserted into the 
sample compartment of the Coleman Model 14 Universal Spectrophotometer and 
the instrument zeroed with the blank solution at a wavelength of 425 
ml I I imicrons. The readings of the sample were taken 5 minutes, 6 minutes, 
and 7 minutes after stirring ceased. After each reading the instrument's 
100% transmittance was reset. A great deal of time was taken to find a 
procedure which would give three consistant galvanometer readings. Several 
problems were overcome by this work. For a long period of time, it was 
unknown why the galvanometer fluctuated continually. This was found to 
14 
be due to the evaporation of the alcohol in the blank over a long period 
of time. This was corrected by shaping a rubber stopper to tightly seal 
the blank cuvette. This stabl ized the galvanometer effectively. Another 
problem found, was that after a short time the barium chloride at such 
concentrations began to cloud when exposed TO air even In the sToppered 
bottle. This was corrected by preparing only smal I quantities of barium 
chloride to provide for fresh clear solutions for each set of determinations. 
TABLE II 
TUBIDIMETRIC SULFATE CALIBRATION CURVE DATA 
Standard Sulfate Water Su Ifate Absorbance Re I ia biii ty 
ml ml ppm Average ppm 
2.0 48.0 4.5 0.068 ±0.2 
4.0 46.0 9.0 0.202 ±0.4 
6.0 44.0 13.6 0.323 ±0.7 
8.0 42.0 18. 1 0.410 ±0.9 
lO.O 40.0 22.6 0.644 ±1.1 
12.0 38.0 27.1 0.785 ±1.3 
14.0 36.0 31.6 0.93+ ±1.6 
Most of the points on the graph I ie on a straight line. The origin 
of the I ine does not I ie on zero parts per mi I (ion. This is due to the 
fact that the solubi I ity product of barium sulfate at 200 C is 2.2 parts 
per mi J I ion, so there is no chance for a zero reading. There are several 
points that do not lie on the line. These points are due to an unknown 
barium sulfate phenomenon. This has been recorded by several people,8 
but considering the accuracy, the points are assumed to I ie on the line. 
15 
The actual plot of barium sulfate curve has an initial slope similar to 
Figure II, but at midrange the slope deviates. 
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CHAPTER til 
DATA AND DATA ANALYSIS 
The map (Figure 2) shows the positions of the wei Is. The number 
ln front of each wei I number Is used in the fol lowing material as a 
shortened form of the standard wei I numbers. The standard wei I numbers 
used In this paper give the location of wei Is according to the fol lowing 
formula: township, range section, 160-acre tract within that section, 
and the 40-acre tract within that quarter section. The 160-acre and 
40-acre tracts are designated a, b, c, and din a counterclockwise 
direction beginning in the northeast quarter. 1 
The data collected for this study was obtained by analysis of 
wei I water samplings taken at varying distances from the Cottonwood and 
Neosho Rivers. Tables 3 through 8 summarize the analytical data collected 
in this investigation. Table 9 lists the precipitation received in the 
Emporia area during the sampling period (January 28 through March 31, 1971) 
as reported by the Federal Aviation Administration Weather Monitor. 
Investigation of Tables 3, 5, and 7 reveal the water type of wei I 
1 to be calcium bicarbonate. This can be accounted for by dissolved I ime­
 stone. The weI I contains only minor amounts of permanent hardness. It 
is of average depth (30 feet) and lies about 150 yards from the Cottonwood 
River. The consistancy of the ionic content tends to show that even with 
moisture change, there was no noticeable change for the aquifer tapped 
by this wei I. 
~~~I-=Ju:~,. !/ q:,h·1d r~, c ~(i 
II n VI) 19 .".. <: ~-
 ..~ ~'. ~c:; 
.. 
x 
, ~. 
. " 11 
18 
FIGURE 3 
WELL LOCATIONS 
18 
41."" SF. It" I (J) 
[~1~f4t:~~t?~if~~t~~9~*~~'
\0~-';,.~/.::--j
 '. I~r, l 1
 .'- ..... 
We I I Numbers 
1­ 19-11-19cb 
2. 19-11-31bc 
3. 19-11-18cc 
4. 19-11-7bc 
5. 18-11-32ad 
6. 18-11-32cd 
7. 18-11-28aa 
8. 18-11-22dc 
9. 19-12-17ab 
10. 19-12-21cd1,. 19-11-30ad 
12. 19-11-36bd 
19 
TABLE 3 
DATA FROM WELLS LOCATED UPSTREAM FROM EMPORIA 
Well 
Number 
Sample 
Number 
Temperature 
of H20 °C(a) 
Acidity 
pH(b) 
Conductivity 
mlcromhos(c) 
Chloride 
ppm (d) 
Chloride 
mI I I Iequ Ivi e) 
1 
2 
3 
* 
9. 1 
11.9 
6.8 
6.8 
7.0 
925 
920 
905 
*** 
*** 
*** 
*** 
*** 
*** 
2 1 
2 
3 
* 
12.4 
12.0 
7.2 
7.2 
6.9 
2660 
2830 
2900 
103 
113 
99 
2.90 
3.20 
2.79 
3 1 
2 
3 
* 
16.6 
17.4 
6.8 
6.8 
6.7 
550 
710 
640 
236 
235 
*** 
6.66 
6.65 
*** 
4 1 
2 
3 
14.0 
12.8 
14.0 
7. 1 
6.9 
6.7 
1105 
1080 
1080 
73 
78 
73 
2.06 
2.22 
2.06 
5 1 
2 
3 
3.3 
4.7 
8.4 
7.3 
6.9 
7.2 
1620 
1810 
1890 
69 
123 
170 
1.97 
3.48 
4.80 
6 1 
2 
3 
11. 1 
** 
** 
7.0 
** 
** 
1015 
** 
** 
191 
** 
** 
5.39 
** 
** 
7 1 
2 
3 
12.3 
12.3 
17.0 
7 •1 
6.9 
7. 1 
786 
758 
780 
36 
41 
39 
1.02 
1. 16 
1. 10 
8 1 
2 
3 
14.5 
22.5 
19.3 
6.8 
6.9 
6.6 
990 
960 
970 
89 
84 
86 
2.50 
2.37 
2.43 
Sample Number 
1 - January 28, 1971 
2 - March 5, 1971 
3 - March 31, 1971 
(a) 
(b) 
(c) 
(d) 
(e) 
±0.050 C 
±0.05 units 
±5 mlcromho 
±5 ppm 
±0.14 milliequiv. 
* 
** 
*** 
No thermometer 
No sample 
Neg I i 9 Ib Ie 
'. 
20
 
TABLE 4
 
DATA FROM WELLS LOCATED DOWNSTREAM FROM EMPORIA
 
Well Sample Temperature Acidity Conductivity Chloride Chloride 
Number Number of H20 °C(a) pH(b) micromhos(c) ppm(d) mi II iequiv.(e) 
9 1 12.6 7.2 1025 *** *** 
2 14.0 6.7 830 *** *** 
3 17.0 6.6 825 *** *** 
10	 1 10.2 7.0 697 69 1.95
 
2 ** ** ** ** **
 
3 14. 1 6.7 1175 86 2.43 
11	 1 13.0 7.0 748 40 1. 13 
2 14.4 6.9 850 42 1. 18 
3 16. 1 6.7 835 43 1. 21 
12	 1 5.3 7.0 295 *** *** 
2 5.4 7.0 320 *** *** 
3 9.4 6.9 330 *** *** 
Sample Number (a) ±0.050C	 ** No sample 
(b) ±0.05 units *** Neg I ig i b Ie 
1 ~ January 28, 1971 (c) ±5 micromhos 
2 - March 5, 1971 (d) ±5 ppm 
3 - March 31, 1971 (e) ±O. 14m i I I iequ iv • 
21 
TABLE 5 
WATER HARDNESS DATA FROM WELLS LOCATED UPSTREAM FROM EMPORIA 
Well 
Number 
Sample 
Number 
Ca+ 2 
ppm 
Mg+2 
ppm 
HC03 ­ppm 
SO4 = ppm 
1 
2 
3 
200±2 
211±2 
221±2 
6±3 
3±5 
0±5 
611±2 
620±2 
617±2 
32± 1.6 
19± 0.9 
14± 0.7 
2 1 
2 
3 
447±2 
523±2 
590±2 
2±5 
2±5 
0±5 
312±3 
329±3 
370±3 
640±30. 
318±24.5 
312±24.5 
3 1 
2 
3 
108±3 
152±3 
160±3 
2±5 
0±5 
1±5 
310±3 
487±2 
485±2 
38± 1.5 
9± 0.4 
10± 0.5 
4 1 
2 
3 
182±3 
187±3 
196±3 
6±3 
0±5 
1±5 
386±3 
411 ±3 
409±3 
71± 4.5 
32± 1.6 
19± 0.9 
5 1 
2 
3 
270±2 
345±2 
578±2 
4±4 
1±5 
1±5 
373±3 
341±3 
341±3 
250±12.5 
97± 4.8 
84± 4.2 
6 1 
2 
3 
175±3 
** 
** 
4±4 
** 
** 
378±3 
** 
** 
100± 5.0 
** 
** 
7 1 
2 
3 
87±4 
91±4 
94±4 
3±5 
2±5 
.1 ±5 
388±3 
413±3 
373±3 
26± 1.2 
12± 0.6 
11± 0.5 
8 1 
2 
3 
103±3 
107±3 
116±3 
5±3 
1±5 
0±5 
379±3 
408±3 
382±3 
39± 2.0 
16± 0.8 
14± 0.7 
Sample Number ** No sample 
1 - January 28, 1971 
2 - March 5, 1971 
3 - March 31, 1971 
22
 
TABLE 6
 
WATER HARDNESS DATA FROM WELLS LOCATED DOWNSTREAM FROM EMPORIA
 
\~ell 
Number 
Sample 
Number 
Ca+2 
ppm 
Mg+2 
ppm 
HCO -3 ppm 
SO = 4 
ppm 
9 1 158±3 2±5 456±2 77±4.7 
2 183±3 4±4 538±2 17±0.8 
3 198±3 1±5 547±2 15±0.7 
10 1 168±3 3±5 370±3 106±5.3 
2 ** ** ** ** 
3 162±3 1±5 459±2 21±1.0 
11 1 172±3 4±4 50212 41±2.0 
2 172±3 6±3 504±2 17±0.8 
3 184±3 1±5 502±2 14±0.7 
12 1 70±4 3±5 212±3 1O± 1.0 
2 63±4 1±5 185±3 8±0.4 
3 70±4 2±5 202±3 7±0.3 
Sample Number ** No sample 
1 - January 28, 1971 
2 - March 5, 1971 
3 - March 31, 1971 
23 
TABLE 7 
HARD WATER DATA FROM WELLS LOCATED UPSTREAM FROM EMPORIA 
Well Sample Ca+2 Mg+2 HC03­ S04= 
Number Number mil I i equ i v. mil I Iequ i v. mil I i equ i v. mil I i equ i v • 
1 9.98±0.05 0.50±0.24 10.01±0.03 0.66±0.03 
2 10.52±0.05 0.24±0.41 10.16±0.03 0.40±0.02 
3 11.04±0.05 0.04±0.41 10.12±0.03 0.29±0.02 
2 1 24.30±0.05 0.16±0.41 5.11±0.05 13.32±0.63 
2 26.08±0.05 O. 16±0. 41 5.39±0.05 6.62±0.51 
3 29.44±0.05 0.04±0.41 6.06±0.05 6.71±0.51 
3 1 5.38±0.07 0.50±0.41 5.08±0.05 1.48±0.03 
2 7.56±0.07 0.04±0.41 7.99±0.03 0.19±0.01 
3 8.00±0.07 0.08±0.41 7.95±0.03 0.21±0.01 
4 1 9.08±0.07 0.16±0.24 6.33±0.05 0.80±0.09 
2 9.32±0.07 0.04±0.41 6.71±0.05 0.67±0.03 
3 9.76±0.07 0.12±0.41 6.30±0.05 0.40±0.02 
5 1 13.48±0.05 0.32±0.33 6.11±0.05 5.20±0.26 
2 17 .20±0.05 0.12±0.41 5.59±0.05 2.02±0.10 
3 28.82±0.05 0.12±0.41 5.59±0.05 1.75±0.87 
6 1 8.74±0.07 0.32±0.33 6.20±0.05 2.08±0.10 
2 ** ** ** ** 
3 ** ** ** ** 
7 1 4.34±0.10 0.24±0.41 6.36±0.05 0.54±0.02 
2 4. 56±0. 10 O. 16±0. 41 6.78±0.05 0.25±0.01 
3 4.68±0.10 0.12±0.41 6.10±0.05 0.23±0.01 
8 1 5.14±0.07 0.42±0.24 6.21±0.05 0.80±0.04 
2 5.36±0.07 0.08±0.41 6.30±0.05 0.33±0.O2 
3 5.80±O.07 O.04±O.41 6.26±0.05 0.29±0.02 
Sample Number ** No sample 
1 - January 28, 1971 
2 - March 5, 1971 
3 - March 31, 1971 
24
 
TABLE 8 
WATER HARDNESS DATA FROM WELLS LOCATED DOWNSTREAM FROM EMPORIA 
Well 
Number 
Sample 
Number 
Ca+2 
mil I i equ iv • 
~1g+2 
milliequlv. 
HC03 ­
 mil I i equ iv . 
SO/ 
mil I iequ iv . 
9 1 7.88±0.07 0.16±0.41 7.47±0.03 j • 60±0. 10 
2 9. 12±0. 07 0.36±0.33 8.82±0.03 0.35±0.02 
3 9.88±0.07 0.12±0.41 8.97±0.03 0.31±0.02 
10 1 3.38±0.07 0.24±0.41 6.06±0.05 2. 20±0. 11 
2 ** ** ** ** 
3 8.08±0.07 O. 12±0. 41 7.52±0.03 0.44±0.02 
11 1 8.58±0.07 0.32±0.33 8.23±0.03 0.86±0.04 
2 8.56±0.07 0.48±0.25 8.27±0.03 0.35±0.02 
3 9.20±0.07 0.08±0.41 8.23±0.03 0.29±0.02 
12 1 3.50±0.10 0.24±0.41 3.47±0.05 0.42±0.02 
2 3. 16±0. 10 0.12±0.41 3.03±0.05 0.17±0.01 
3 3.48±0.10 O. 16±0. 41 3.31±0.05 0.15±0.01 
-
 Sample Number ** No sample 
1 - January 28, 1971 
2 - March 5, 1971 
3 - March 31, 1971 
25 
TABLE 9
 
PRECIPITATION IN THE EMPORIA AREA
 
FROM JANUARY 28, THROUGH MARCH 31, 1971, AS REPORTED BY
 
THE FEDERAL AVIATION ADMINISTRATION WEATHER MONITOR
 
Inches of Inches of 
Date Ra i nfa II Date Ra i nfa II 
January 28 0.00 March 1 trace 
29 0.00 2 0.00 
30 trace 3 0.00 
31 trace 4 0.00 
February 1 0.01 5 0.00 
2 0.00 6 0.00 
3 0.00 7 0.00 
4 0.40 8 0.00 
5 0.01 9 0.06 
6 0.00 10 0.00 
7 0.00 11 0.00 
8 0.00 12 0.00 
9 0.00 13 0.00 
10 0.00 14 trace 
11 0.06 15 0.00 
12 0.00 16 0.00 
13 0.00 17 0.00 
14 0.00 18 trace 
15 0.00 19 trace 
16 0.00 20 0.00 
17 0.00 21 0.00 
18 0.26 22 0.00 
19 trace 23 0.00 
20 0.00 24 0.20 
21 0.56 25 trace 
22 0.23 26 0.00 
23 0.00 27 0.00 
24 0.00 28 0.00 
25 0.00 29 0.00 
26 0.00 30 0.00 
27 0.00 31 0.00 
28 0.08 
26
 
The water type of wei I 2 (Tables 3, 5, and 7) was calcium 
bicarbonate and sulfate. This was the hardest of the waters analyzed. 
The wei I was located to the south of the terrace gravel and alluvium. 
The wei I was .of the low water productivity type so the slower moving 
water may collect more minerals. 
The water type of well 3 (Tables 3, 5, and 7) was primarily cal­
 cium bicarbonate. The first two samples yielded a high chloride con­
 tent, but this disappeared almost entirely for the third sample. The 
calcium and bicarbonate increases were constantly in a ratio of 1:1, 
showing the increase by more dissolved limestone. 
The water type of wei I 4 (Tables 3, 5, and 7) was calcium bicar­
 bonate. There was a relatively constant chloride concentration with some 
sulfate present. The changes In the sample's ionic content did not 
correlate with precipitation records (Table 9). 
The water type of wei I 5 (Tables 3, 5, and 7) was a mixture of 
calcium bicarbonate, sulfate, and chloride. There is no apparent reason 
for the great Influx of calcium Ion or the erratic fluctuation of the 
relatively high concentration of the sulfate and chloride. The weI I 
is located off the Neosho river terrace gravels. It is about 30 feet 
deep and a low productivity wei I. 
The water type of well 6 (Tables 3,5, and 7) was a mixture of 
calcium bicarbonate, sulfate, and chloride. The reason for the one 
sampling is that the occupants of the house at which the samples were 
taken were not at the house during the day of samplings or 3 subsequent 
times. 
The water type of wei I 7 (Tables 3, 5, and 7) was calcium bicar­
 bonate. There was I ittle permanent hardness found In this water. The 
27
 
weI I was being used during each of the sampl ings. The samples were 
taken after 200 to 500 gallons of water had been discharged. The smal f 
changes In concentration may have been due to,the inflow of surrounding 
water. 
The water type of weI I 8 (Tables 3, 5, and 7) was calcium bicar­
 bonate. It is the sole source of water for a trailer park located north 
of Emporia. The lack of significant changes for the data could be due 
to the high productivity of the wei I • 
The water type of wei I 9 (Tables 4, 6, and 8) was calcium bicar­
 bonate.One reason for Increased calcium bicarbonate content could be an 
Increased solubility with the increased water temperature. The wei I is 
only 50 yards from the Neosho River. 
The water type of wei I 10 (Tables 4, 6, and 8) was calcium bicar­
 bonate. There was a marked Increase in calcium and bicarbonate over the 
span of time. The first sampl ing indicated a relatively high sulfate 
content. The reason for the lack of a second sample was that at that 
time the quarter ml Ie driveway leading to the farmhouse was blocked by 
mud and the farmer was not at home. 
The water type of wei I 11 (Tables 4, 6, and 8) was calcium bicar­
 bonate. The only noticeable change in ionic concentrations was a drop in 
sulfate concentration. 
The water type of well 12 (Tables 4,6, and 8) was calcium bicar­
 bonate. This weI I was located south of Emporia on a hi I I. The wei I pro­
 duces the softest water of al I the wei Is sampled. 
The individual well analysis shows that the predominant ions pre­
 sent in the waters are calcium and bicarbonate. Assuming the source of 
28 
the calcium to be attributed to be only dissolved I imestone, there should 
be an equal number of equivalents of bicarbonate present. A plot of 
mil I iequlvalents of calcium vs. mil I lequivalents of bicarbonate should 
yield a straight line (Figure 3). The experimental data from this study 
shows that upstream from Emporia and Just off the south side of the 
terraces of the respective rivers, there Is an increase in calcium which 
shows no increase in bicarbonate Ion. The reasons for these differences 
are not evident from the data collected during this study. The remainder 
of the sample points lie on or near the line. 
There is a characteristic of wei Is several mi les north of the 
rivers on the upstream side of Emporia. They have between 6.0 and 6.8 
mil I iequivalents of bicarbonate. The calcium concentration for these 
wei Is differ In that wei I 4 has as much calcium as most of the wei Is. 
Wei Is 7 and 8 have lower calcium concentrations. More data wil I need 
to be collected before general conclusions would be warranted regarding 
chloride ion. The chloride content ranged from a lower I imit undetect­
 able by the method used (below 1 mil I iequivalent) to an upper limit of 
6.66 ml Illequivalents. 
• • • • 
29 
12 
11 ~ •~ 
10 l • 
• 
9~ ."Lm _•
 
c-~ 8 /.
 
o ' 
-L 
+- m 7 
ro 0­
 L 
+- III 
C +- 6m c 
u m 
c-
 o ro 
U > 5 
N ::J 
+ 0­
 ro m' 
u- 4 
E 
..... 3 
2 
o V I , , I , , I , , , ' 
o 2 3456789 10 11 12 
HC03- Concentration
 
Cml I llequlvalents per I iter)
 
FIGURE 4 
CONCENTRATION OF CA+2 V5. CONCENTRATION OF HC03 
CHAPTER IV 
DISCUSSION 
The purpose of this investigation was to complete the prel imlnary 
analysis of ground water In the vicinity of Emporia, Kansas~ and to deter­
 mine If the terrain on the upriver and downriver sides of Emporia would 
yield a decrease or Increase of the hardness mineral content. The data 
collected infers that the predominant ions detected in this study were 
calcium and bicarbonate. These Ions would be present in water found 
running through beds of I imestone. Limestone is the most common bedrock 
in the area, so any ground water flowing In this vicinity should contain 
varying amounts of calcium and bicarbonate as control led by temperature, 
water velocity, acidity, etc. The other ions tested in this study appear 
to have been due to sporadic contamination of the ground waters coming 
from many possible sources. 
The multiple samplings helped in evaluation of changes In ionic 
concentrations. The data shows some possible trends as to ion concentra­
 tion differences. While most wei Is showed sl ight changes as to total 
, 
ion concentration, most wei Is could be classified as to type hardness 
based on ea+2/HC03- ratios. More extensive studies wi I I be required to 
draw a definite conclusion as to the meaning of the data concerning 
sources of the other Ions Investigated. Differences in ion content for 
the two watersheds were encountered in this study. A better understanding 
of the source of ions would probably have been obtained by more extensive 
monitoring of wells. 
31 
The problem investigated in this study has importance in that it 
is the most extensive analysis of ground water in the Emporia area. 
AHdVCl80118 18
 
BIBLIOGRAPHY 
(1)	 O'Connor, Howard G. Geology, Mineral Resources, and Ground vlater 
Resources 2l Lyon County, Kansas. Part 3. Lawrence: Univer­
 sity of Kansas Pubi ications, 1953. 
(2)	 American Publ ic Health Association et al., comp., Standard Methods 
for the Examination of Water end Industrial Wastes. Thirteenth 
Edition. New York: American Health Association, Inc., 1966. 
(3)	 Skoog, Douglas A. and Donald M. \·Jest. Fundamentals of Analytical 
Chemistry. Second Edition. New York: Holt, Rinehart, and 
Winston, Inc., 1969. 
(4)	 Kalthoff, I. M. and E. B. Sandel I. Textbook of Quantitative Inorganic 
Analysis. Third Edition. New York: MacMi I Ian, Inc., 1953. 
(5)	 Meloan, CI if ton and Robert W. Kiser. Problems and Experiments ~ 
Instrumental Analysis. Columbus: Merrl I I Publishing, 1966. 
(6)	 Ros In, Joseph. Reagent Chemicals and Standards. Fourth Edition. 
Princeton: D. Van Nostrand, 1961. 
(7)	 Golterman, H. L. Methods for Cheml~.al Analysis of Fresh Water. 
IBP Handbook No.8, London: . Biockwei I Scientific Publ ica-dons, 
1970. 
(8) Llteanu, Candin and Harold Lingner. Talanta, 17:1045, 1970.