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Sasha Neely

4/12/18
CHEM 113: Experimental Chemistry II
Section 004
TA Justin Munro

Group Members:
1) Sasha Neely, Seat 169
2) Lasair ni Chochlain, Seat 170
3) Mary Patterson, Seat 175
4) Selma Paul, Seat 176

Exp. 10: Chemistry of Natural Waters


Formal Lab Report
2

INTRODUCTION

Hardness of water is determined by the concentration of divalent cation compounds in a

given sample. While numerous polyvalent cations can impart the specific chemical properties

associated with “hardness,” the most common contributing compounds are magnesium and

calcium. These elements are abundantly present in the natural mineral composition of soil and

rock. When water (the universal solvent) comes into contact with these inorganic substances, the

metallic cations are conferred by the dissolved deposits.1

While the drinking of hard water is not associated with human health problems, it does

play a role in other social complications.2 On the individual level, hard water interferes with

daily cleansing routines by decreasing the effectiveness of synthetic soaps and detergents.

Operations of industry are also inhibited due to the buildup of scale, the precipitate of divalent

cation compounds that result from high-temperature usage in pipes. Scale increases blockages

while decreasing water flow efficiency, culminating in higher energy costs and shorter-lived

infrastructure.3 These problems, among others, warrant an examination of the ions that determine

water hardness.

There are two primary ways to determine the hardness of a water sample. The more cost-

effective method involves a titration process with the chelating agent ethylenediaminetetraacetic

acid, henceforth referred to as EDTA. In this procedure, a pH-adjusted water sample is combined

with the metal ion indicator Eriochrome black T, or EBT. In this buffered, basic environment of


1
The USGS Water Science School, USGS: Science for a Changing World. Water Properties
Home: Water Hardness. https://water.usgs.gov/edu/hardness.html (accessed Mar 22, 2018).
2
Cotruvo, J.; Bartram, J. eds. Calcium and Magnesium in Drinking Water: Public Health
Significance. Geneva, World Health Organization, 2009.
3
Drinking Water: Hard Water. City of Cambridge, MA [Online].
http://www2.cambridgema.gov/CityOfCambridge_Content/documents/Drinking%20WaterMy%
20edition.pdf (accessed Mar 30, 2018).
3

approximately pH 10, EBT is in its HD2- form and appears sky-blue in color. While Ca2+ will not

react with the indicator, Mg2+ ions in the sample will become MgD- and the beginning solution

thus becomes a characteristic wine-red. As EDTA is then added, the end point of the titration

will occur when all of the Ca2+ and Mg2+ ions have reacted with the EDTA to form colorless

chelates. The solution will return to a sky-blue color, indicative of the EBT indicator losing its

Mg2+ ions and returning to its HD2- structure.4 Using the end point of the titration, the total

divalent cation content can be found and converted into ppm CaCO3, a measure of water

hardness.

Atomic Absorption Spectrophotometry (AA) is another technique used to measure water

hardness of a given sample. AA is based on the chemical principle that each atom has its own

discrete electronic energy level. For any atom to absorb the energy of light that falls upon it, the

energy of the photons must equal the difference in energy between two of the atom’s electronic

energy levels.5 This concept led to the development of the atomic absorption spectrophotometer.

This instrument projects light of a single wavelength, matching the energy separation of the

atoms of interest, through the water sample. The amount of light absorbance will be proportional

to the concentration of that specific type of atom. If the absorbance measurement falls within the

standards of the instrument’s initial calibration used to check the accuracy/reproducibility of the

apparatus, the Beer-Lambert law can be used to calculate the unknown metal concentration in the


4
Community College of Rhode Island, Chemistry Courses: Labs, Calcium Analysis by EDTA
Titration.
http://www.ccri.edu/chemistry/courses/chem_1100/wirkkala/labs/Calcium_Analysis_by%20ED
TA_Titration.pdf (accessed April 10, 2018).
5
Sevostianova, Elena. New Mexico State University, Introduction: Atomic Absorption
Spectroscopy. https://web.nmsu.edu/~esevosti/report.htm (accessed Mar 30, 2018).
4

sample.6 If the absorbance measurement exceeds 1 absorbance unit, only a small amount of light

was successfully transmitted through the atoms. Dilution of the water sample will be necessary

to obtain an accurate reading before the Beer-Lambert law can be applied.

In this project, both EDTA titration and AA Spectrophotometry were used to determine

the hardness of four distinct water samples. The water was obtained from different sources

throughout the state of Pennsylvania - river water from the Delaware River; pond water from

Bullfrog Valley Pond in Hummelstown, PA; tap water from a home in Macungie, PA; and well

water from a home in Zionsville, PA. The Delaware River water will be soft because the river is

fed by streams and creeks that flow through the high mountains of Appalachia. Due to the steep

slopes and thin soil cover on the ground, rain runoff quickly reaches the tributaries without

sinking into the earth and dissolving its rock.7 Because the Bullfrog Valley Pond water is

similarly supplied by a brook, it too will be classified as soft. In contrast, the Macungie tap water

and Zionsville well water will both be hard. These towns are located in the Lehigh Valley of

southeastern Pennsylvania, a region which contains the high-calcium limestones of the Kinzers,

Annville, Benner, and Keyser formations.8 The area also contains a high concentration of

dolomite rock, a sedimentary mineral consisting of calcium and magnesium carbonate.9


6
Thompson, S. PSU Chemtrek: Small-Scale Experiments for General Chemistry. Keiser, J. Ed.;
Hayden-McNeil Publishing; Plymouth, MI 2017. pp. 10-1 to 10-24.
7
McCarthy, L. T.; Keighton, W. B.; Quality of Delaware River Water at Trenton, New Jersey.
Geological Survey Water-Supply Paper 1779-X. [Online] 1964.
https://pubs.usgs.gov/wsp/1779x/report.pdf (accessed April 5, 2018).
8
Limestone and Dolomite Distribution in Pennsylvania. Bureau of Topographic and Geologic
Survey, Fourth Edition, 1990; Third Printing. [Online] Revised, 2000. http://www.water-
research.net/Waterlibrary/geologicdata/map15.pdf (accessed April 8, 2018).
9
Geologic Map of Pennsylvania. Commonwealth of Pennsylvania Department of Conservation
and Natural Resources. Bureau of Topographic and Geologic Survey, Third Edition, 1990;
Fourth Printing. [Online] Revised, 2007.
http://www.docs.dcnr.pa.gov/cs/groups/public/documents/document/dcnr_016205.pdf (accessed
April 8, 2018).
5

PROCEDURE

Four water samples were analyzed using the procedure outlined in Experiment 10: The

Chemistry of Natural Waters.6 The table on the following page identifies and describes these

samples.

Table 1: Description of the Experimental Water Samples

Identification Dilution Dilution Filtered Lab Partner


for AA for EDTA

Pond Water10 No No No Sasha Neely


Bullfrog Valley Pond, PA Seat 169, pp. 34-37

River Water11 No No No Selma Paul


Delaware River, PA Seat 176, pp. 31-33

Tap Water12 1:1 1:1 No Lasair ni Chochlain


Home in Macungie, PA Seat 170, pp. 40-56

Well Water13 1:1 1:1 No Mary Patterson


Home in Zionsville, PA Seat 175, pp. 51-53

The water samples were first examined using Atomic Absorption spectroscopy. Two

instruments were used – one for the Ca2+ analysis, the other for the Mg2+ analysis. The pond

water and river water were measured without dilution, while the tap water and well water were


10
Neely, S. Seat 169, pp. 34-37. Pond water sample, Bullfrog Valley Pond, PA.
11
Paul, S. Seat 176, pp. 31-33. River water sample, Delaware River, PA.
12
Chochlain, L. Seat 170, pp. 40-56. Tap water sample, Macungie, PA.
13
Patterson, M. Seat 175, pp. 51-53. Well water sample, Zionsville, PA.
6

both diluted at a 1:1 ratio with distilled water. Droplets of the undiluted samples were then

evaporated to determine the concentration of total dissolved solids in the water. To do this, three

distinct droplets were placed on the shiny side of a piece of aluminum foil. One drop was the

undiluted water sample, the other drop was distilled water, and the final drop was 1.00 X 10-3 M

Ca2+. Placing the foil on a hot plate, the droplets were allowed to evaporate. The white solids that

remained were the nonvolatile salts that were originally in the solutions. These were observed,

noted, and compared.

The next procedures involved divalent cation analysis by EDTA titration. Before

analyzing the water samples directly, a practice serial titration with a known amount of Ca2+ (aq)

was carried out. One drop of 1.00 X 10-3 M Ca2+ solution was added to each of the 12 wells in a

clean 1 X 12 well strip along with one drop of the EBT indicator and one drop of the

NH3/NH4Cl/MgEDTA buffer. From there, a serial titration was done with the EDTA solution (1

drop of the 2.00 X 10-4 M EDTA to the first well, 2 drops to the second, and so on). The end

point (the first sky-blue well) was noted and the concentration of the original solution was

calculated. This process was repeated in another titration, the only change being the addition of

one drop of a 1.00 X 10-3 M Mg2+ solution to the one drop of the 1.00 X 10-3 M Ca2+ solution.

After this preparation, the EDTA titration was done on the four water samples. The same

serial titration process was used, however, one drop of the water sample replaced the known

concentrations of Ca2+ and Mg2+ that were used in the previous titrations. It should be noted that

the pond and river water samples remained undiluted, while the 1:1 dilutions of the tap and well

water samples (mentioned previously in the evaporation test of the procedure) were used. After a

duplicate analysis was carried out and the average of the two EDTA titrations was determined,
7

the concentration of the divalent cations was calculated and converted into the typical

measurement of water hardness – ppm CaCO3.

Finally, the divalent cations of the water samples were removed through the process of

ion exchange. A small amount of the water sample was added to a vial containing cation

exchange resin. The vial was secured and then shaken vigorously for approximately a minute. A

serial titration was then carried out with one droplet of the resulting supernatant liquid. After a

duplicate analysis was done, the average of the two EDTA titrations was used to calculate the

hardness of the resin-treated water sample.

RESULTS

Table 2: Comparison of TDS Residue after Water Evaporation from 1 Drop of Sample

Sample Observation

Distilled water10 No residue

1.00 X 10-3 M Ca2+ (reference)10 Faint ring

Bullfrog Valley Pond Water11 Visible white ring, slightly more than reference

Delaware River Water12 Faint ring, comparable to reference

Macungie Tap Water13 Fully opaque white ring, more than reference

Zionsville Well Water14 Faint ring, comparable to reference


8

Table 3: Atomic Absorption Spectrophotometer Standards for Ca2+

Date: 3/15/2018

Time: 6:20 PM

AA Operator: K. Brown

Ca2+ Concentration (ppm) Absorbance Value (at 422.7 nm) Check Standard (ppm)

1.000 0.00451 1.40

5.00 0.03080 4.72

10.00 0.05401 9.84

25.0 0.12485 24.59

50.0 0.25189 50.04

Graph 1: Atomic Absorption Calibration Plot for Ca2+

AA Calibration Plot for Ca2+


0.3
Absorbance Value at 422.7 nm (nm)

0.25

0.2

0.15
y = 0.005x + 0.0027
0.1

0.05

0
0 10 20 30 40 50 60
Concentration of Ca2+ (ppm)
9

Table 4: Atomic Absorption Spectrophotometer Standards for Mg2+

Date: 3/15/2018

Time: 6:20 PM

AA Operator: K. Brown

Mg2+ Concentration (ppm) Absorbance Value (at 202.5 nm) Check Standard (ppm)

1.000 0.01057 1.43

5.00 0.07621 4.53

10.00 0.14025 9.39

25.0 0.28809 24.75

50.0 0.33022 30.21

Graph 2: Atomic Absorption Calibration Plot for Mg2+

AA Calibration Plot for Mg2+


0.4
Absorbance Value at 422.7 nm (nm)

0.35
0.3
0.25
y = 0.0063x + 0.0536
0.2
0.15
0.1
0.05
0
0 10 20 30 40 50 60
Concentration of Mg2+ (ppm)
10

Sample Calculation of Ca2+ Concentration from AA Calibration Plot

! = 0.005& + 0.0027

! − 0.0027
&=
0.005
0.1278 − 0.0027
&= = 25.02 ../
0.005

Table 5: Initial Ca2+ Concentration from AA Calibration Plot

Water Sample Absorbance Ca2+ Concentration (ppm)

Bullfrog Valley Pond Water11 0.1278 25.02

Delaware River Water12 0.0758 14.62

Macungie Tap Water13 0.1104 21.54 X 2 = 43.08*

Zionsville Well Water14 0.1629 32.04 X 2 = 64.08*

* Note: 1:1 diluted samples were multiplied by 2 to get the concentration of the original sample

Sample Calculation of Conversion from ppm Ca2+ to ppm CaCO3

100.09 5 01067 1 /89:


25.02 ../ 0123 = 62.48 ../ 01067
1 /89: 40.08 5 0123
11

Table 6: Conversion of Ca2+ Concentration to ppm CaCO3

Water Sample Ca2+ Concentration (ppm) CaCO3 (ppm)

Bullfrog Valley Pond Water11 25.02 62.48

Delaware River Water12 14.62 36.51

Macungie Tap Water13 43.08 107.6

Zionsville Well Water14 64.08 160.0

Sample Calculation of Mg2+ from AA Calibration Plot

! = 0.0063& + 0.0536

! − 0.0536
& =
0.0063

0.1705 − 0.0536
&= = 18.56 ../
0.0063
12

Table 7: Initial Mg2+ Concentration from AA Calibration Plot

Water Sample Absorbance Mg2+ Concentration (ppm)

Bullfrog Valley Pond Water11 0.1705 18.56

Delaware River Water12 0.0710 2.762

Macungie Tap Water13 0.1377 13.35 X 2 = 26.70*

Zionsville Well Water14 0.0320 -3.429 X 2 = -6.857*

* Note: 1:1 diluted samples were multiplied by 2 to get the concentration of the original sample

Sample Calculation of Conversion from ppm Mg2+ to ppm CaCO3

100.09 5 01067 1 /89:


18.56 ../ >523 = 76.42 ../ 01067
1 /89: 24.31 5 >523

Table 8: Conversion of Mg2+ Concentration to ppm CaCO3

Water Sample Mg2+ Concentration (ppm) CaCO3 (ppm)

Bullfrog Valley Pond Water11 18.56 76.42

Delaware River Water12 2.762 11.37

Macungie Tap Water13 26.70 109.9

Zionsville Well Water14 -6.857 -28.23


13

AA Total Water Hardness Sample Calculation

Pond Water total hardness value = 62.48 ppm CaCO3 + 76.42 ppm CaCO3
= 138.9 ppm CaCO3

Table 9: AA Total Hardness Value for the Water Samples

Water Sample Total CaCO3 (ppm)

Bullfrog Valley Pond Water11 138.9

Delaware River Water12 47.88

Macungie Tap Water13 217.5

Zionsville Well Water14 131.77

Table 10: EDTA Serial Titration Observed Endpoint

Water Sample Well Number (drops)

Bullfrog Valley Pond Water11 7 and 9


Average: 8

Delaware River Water12 5

Macungie Tap Water13 8

Zionsville Well Water14 7


14

Sample Calculation for Molarity of Divalent Cations in a Water Sample

>?@AB C?@AB = >DEFGHIJK LGKEMJN CDEFGHIJK LGKEMJN

2.00 × 10PQ > RSTU (8 WX8.Y)


>DEFGHIJK LGKEMJN =
1 WX8.

>DEFGHIJK LGKEMJN = 1.60 × 10P7 >

Conversion of Divalent Cation Molarity to ppm CaCO3

1.60 × 10P7 /89:Y 01067 100.0 5 01067 1000 /5 01067


= 160. ../ 01067
1 9[\:X 8] Y89^\[8_ 1 /89: 01067 1 5 01067

Table 11: EDTA Serial Titration Results for the Water Samples

Water Sample Divalent Cations (M) CaCO3 (ppm)

Bullfrog Valley Pond Water11 1.60 X 10-3 160.*

Delaware River Water12 1.00 X 10-3 100.

Macungie Tap Water13 1.60 X 10-3 160.

Zionsville Well Water14 1.40 X 10-3 140.

*Note: This was calculated from the average endpoint


15

Table 12: Range of Water Hardness Values

Water Sample CaCO3 (ppm)

Bullfrog Valley Pond Water11 139 - 180.

Delaware River Water12 48.0 - 100.

Macungie Tap Water13 160. - 218

Zionsville Well Water14 132 - 140.

Table 13: Divalent Cation Removal by Ion Exchange EDTA Serial Titration

Water Sample Observed Endpoint (drops) Total CaCO3 (ppm)

Bullfrog Valley Pond Water11 2 40.0

Delaware River Water12 2 40.0

Macungie Tap Water13 2 40.0

Zionsville Well Water14 2 40.0


16

Sample Calculation for Percent Change of Water Sample Hardness

../ 01067 8] RSTU 8X[5[_19 Y1/.9: − ../ 01067 8] Y8]\:_:W Y1/.9:


= & 100%
../ 01067 8] RSTU 8X[5[_19 Y1/.9:

[160. ../] − [40.0 ../]


= & 100% = 75% cℎ1_5:
160. ../

Table 14: Percent Change of Water Sample Hardness

Water Sample Original CaCO3 Softened CaCO3 Percent Change


(ppm) (ppm)

Bullfrog Valley Pond 160. 40.0 75%


Water11

Delaware River Water12 100. 40.0 60%

Macungie Tap Water13 160. 40.0 75%

Zionsville Well Water14 140. 40.0 71.4%

Table 15: pH of Water Sample Before/After Cation Removal by Ion Exchange

Water Sample pH Before pH After

Bullfrog Valley Pond Water11 6 2

Delaware River Water12 7 2

Macungie Tap Water13 6.5 2

Zionsville Well Water14 8 2


17

DISCUSSION

Classification of water hardness, related to mg/L of CaCO3 by the United States

Geological Survey, is as follows: 0-60 mg/L CaCO3 is soft, 61-120 mg/L is moderately hard,

121-180 mg/L is hard, and more than 180 mg/L is very hard.14 According to these guidelines and

the ranges calculated through the AA and EDTA experiments, the relative hardness of the four

water samples can be determined. The results illuminated that the river water was soft, the well

water was hard, the pond water was harder, and the tap water was very hard/hardest.

This scale was not exactly what was expected. The main difference from the original

hypothesis was that the pond water came back as being harder than the well water. There are a

few possible explanations for this development. On the qualitative level, the Bullfrog Valley

Pond where the water was collected is located in Dauphin County, Pennsylvania. The same

limestone and dolomite deposits that run below the ground of the Lehigh Valley are present in

the soil of the Dauphin region.9 While the pond is fed by a very small creek, it is largely made up

of standing water. It thus has more time in contact with the surrounding soil and rock, dissolving

greater amounts of mineral solids into its solution.

Conversely, the well water could be softer than expected because of its construction.

Private wells such as the one from which the Zionsville sample was taken are cased within the

ground. This casing prevents groundwater contaminants from entering the well and mixing with

the drinking water.15 Due to this structural component, the well water has a set number of


14
USGS Water-Quality Information, USGS: Science for a Changing World. Water Hardness and
Alkalinity: Water Hardness. https://water.usgs.gov/owq/hardness-alkalinity.html
(accessed Mar 22, 2018).
15
Private Wells, United States Environmental Protection Agency. Learn About Private Water
Wells: Well Components. https://www.epa.gov/privatewells/learn-about-private-water-wells
(accessed April 3, 2018).

18

dissolved solids in the water system. The water does not continuously dissolve the surrounding

ground minerals because it does not come into contact with them after a certain time.

The Delaware River water was the softest, as was expected. This conclusion was

bolstered by the timing of the water sample collection. The water sample was taken from the

river in early spring (March) after a particularly bad winter storm brought an accumulation of

10+ inches of snow to central and southeast Pennsylvania.16 This snow was in the process of

melting and inundating the tributaries that lead to the Delaware River. The higher flow rate

resulted in fewer total dissolved solids, as has been historically documented.7

The Macungie tap water was the hardest, also the result that was expected. According to

the Borough of Macungie water parameters, its water has a Ca2+ hardness of 13.3 grains per

gallon.17 When converted to ppm, this is a hardness of approximately 228 ppm CaCO3. This

measurement is a little more than the range which was calculated for the tap water (160 – 218

ppm CaCO3). This brings up the quantitative differences of the experiments that were carried

out.

The EDTA serial titration naturally resulted in a higher CaCO3 ppm measurement

because it is a technique used to find out the total divalent cation concentration in a solution. It

does not discriminate between polyvalent ions and takes into account all of them, not just the

Ca2+ and Mg2+ ions that are responsible for water hardness. Pennsylvania geologic records

include sandstone and shale formation, which contributed to the polyvalent cation content of the


16
Lehigh Valley Live, Lehigh Valley Weather. Lehigh Valley is in ‘Jackpot’ Area for
03/07/2018 Snowstorm.
http://www.lehighvalleylive.com/weather/index.ssf/2018/03/lehigh_valley_is_jackpot_area_for_
03072018_snowsto.html (accessed Mar 25, 2018).
17
Borough of Macungie, Borough Water Parameters, Borough Test Results: Calcium Hardness.
http://macungie.pa.us/drinkingwater.htm (accessed April 15, 2018).
19

water samples.18 In contrast, the Atomic Absorption Spectrophotometry technique only measured

the concentration of one type of cation at a time and was thus a smaller, more specific hardness.

EDTA as a whole is relatively precise. In three of the four sample titrations, the duplicate

analysis matched the original. However, in the pond water sample, one endpoint occurred at well

7 while the other occurred at well 9. Because each drop of EDTA corresponded to a change of

20.0 ppm CaCO3, the hardness value would change by that number if there were a one well

difference. By EDTA, the pond water consequently had a range of 139 – 180. ppm CaCO3.

EDTA was not only precise, it was also quite accurate in this experiment. When determining the

concentration of the known Ca2+ and Mg2+ solution, it only had a percent error of 20%. For a

general overview of the water sample composition, EDTA offered a scientifically sound, cost-

effective, and easy method.

Atomic Absorption Spectrometry also had a high degree of accuracy in this project. The

percent errors of the check standards are outlined in the tables on the next page. In summary, the

percent error of the AA spectrophotometer did not exceed 43% for any of the standards. For

most of the standards, the percent error was much lower. The AA instrument can thus be trusted

to be accurate in the analysis of the four water samples that were tested.


18
Barnes, J. H.; Sevon, W. D. The Geological Story of Pennsylvania. Commonwealth of
Pennsylvania Department of Conservation and Natural Resources. Bureau of Topographic and
Geologic Survey. [Online] Educational Series 4, 2014.
http://www.docs.dcnr.pa.gov/cs/groups/public/documents/document/dcnr_014597.pdf
(accessed April 11, 2018).

20

Table 16: Ca2+ Check Standards Percent Error

Ca2+ Concentration (ppm) Check Standard (ppm) Percent Error (%)

1.000 1.40 40.%

5.00 4.72 5.6%

10.00 9.84 1.6%

25.0 24.59 1.6%

50.0 50.04 0.080%

Table 17: Mg2+ Check Standards Percent Error

Mg2+ Concentration (ppm) Check Standard (ppm) Percent Error (%)

1.000 1.43 43%

5.00 4.53 9.4%

10.00 9.39 6.1%

25.0 24.75 1.0%

50.0 30.21 40.%


21

CONCLUSION

Of the four water samples that were tested, the Delaware River water was the softest, the

Zionsville well water was the next softest, the Bullfrog Valley Pond water was hard, and the tap

water from Macungie was the hardest. These results were not what was expected, but can be

explained due to the geologic trends of the state of Pennsylvania, the specific construction of

well water pipes, and recent meteorological events to the sampling period.
22

REFERENCES

In numerical order:

1. The USGS Water Science School, USGS: Science for a Changing World. Water Properties
Home: Water Hardness. https://water.usgs.gov/edu/hardness.html (accessed Mar 22, 2018).

2. Cotruvo, J.; Bartram, J. eds. Calcium and Magnesium in Drinking Water: Public Health
Significance. Geneva, World Health Organization, 2009.

3. Drinking Water: Hard Water. City of Cambridge, MA [Online].


http://www2.cambridgema.gov/CityOfCambridge_Content/documents/Drinking%20WaterMy%
20edition.pdf (accessed Mar 30, 2018).

4. Community College of Rhode Island, Chemistry Courses: Labs, Calcium Analysis by EDTA
Titration.
http://www.ccri.edu/chemistry/courses/chem_1100/wirkkala/labs/Calcium_Analysis_by%20ED
TA_Titration.pdf (accessed April 10, 2018).

5. Sevostianova, Elena. New Mexico State University, Introduction: Atomic Absorption


Spectroscopy. https://web.nmsu.edu/~esevosti/report.htm (accessed Mar 30, 2018).

6. Thompson, S. PSU Chemtrek: Small-Scale Experiments for General Chemistry. Keiser, J. Ed.;
Hayden-McNeil Publishing; Plymouth, MI 2017. pp. 10-1 to 10-24.

7. McCarthy, L. T.; Keighton, W. B.; Quality of Delaware River Water at Trenton, New Jersey.
Geological Survey Water-Supply Paper 1779-X. [Online] 1964.
https://pubs.usgs.gov/wsp/1779x/report.pdf (accessed April 5, 2018).

8. Limestone and Dolomite Distribution in Pennsylvania. Bureau of Topographic and Geologic


Survey, Fourth Edition, 1990; Third Printing. [Online] Revised, 2000. http://www.water-
research.net/Waterlibrary/geologicdata/map15.pdf (accessed April 8, 2018).

9. Geologic Map of Pennsylvania. Commonwealth of Pennsylvania Department of Conservation


and Natural Resources. Bureau of Topographic and Geologic Survey, Third Edition, 1990;
Fourth Printing. [Online] Revised, 2007.
http://www.docs.dcnr.pa.gov/cs/groups/public/documents/document/dcnr_016205.pdf (accessed
April 8, 2018).

10. Neely, S. Seat 169, pp. 34-37. Pond water sample, Bullfrog Valley Pond, PA.

11. Paul, S. Seat 176, pp. 31-33. River water sample, Delaware River, PA.

12. Chochlain, L. Seat 170, pp. 40-56. Tap water sample, Macungie, PA.

13. Patterson, M. Seat 175, pp. 51-53. Well water sample, Zionsville, PA.
23

14. USGS Water-Quality Information, USGS: Science for a Changing World. Water Hardness
and Alkalinity: Water Hardness. https://water.usgs.gov/owq/hardness-alkalinity.html
(accessed Mar 22, 2018).

15. Private Wells, United States Environmental Protection Agency. Learn About Private Water
Wells: Well Components. https://www.epa.gov/privatewells/learn-about-private-water-wells
(accessed April 3, 2018).

16. Lehigh Valley Live, Lehigh Valley Weather. Lehigh Valley is in ‘Jackpot’ Area for
03/07/2018 Snowstorm.
http://www.lehighvalleylive.com/weather/index.ssf/2018/03/lehigh_valley_is_jackpot_area_for_
03072018_snowsto.html (accessed Mar 25, 2018).

17. Borough of Macungie, Borough Water Parameters, Borough Test Results: Calcium
Hardness. http://macungie.pa.us/drinkingwater.htm (accessed April 15, 2018).

18. Barnes, J. H.; Sevon, W. D. The Geological Story of Pennsylvania. Commonwealth of


Pennsylvania Department of Conservation and Natural Resources. Bureau of Topographic and
Geologic Survey. [Online] Educational Series 4, 2014.
http://www.docs.dcnr.pa.gov/cs/groups/public/documents/document/dcnr_014597.pdf
(accessed April 11, 2018).