Sei sulla pagina 1di 22


William Alexander Beam

6 April, 2017

Experiment 10 Formal Lab Report

Chemistry 113 Section 003

In collaboration with: Alicia Ali, Cameron Arthur, and Kelcie Allen

Supervising TA: Saehyun Choi



In regards to water quality, the term hardness refers to the overall composition

of the water, including minerals that are comprised within a given sample through natural

dissolution. Water samples with low concentrations are considered soft while samples

with high concentrations are considered hard. More specifically, through the natural

flow of water in an environment, dissolution of polyvalent, metallic elements occurs as

the water passes over various rocks and soil 1 . The presence of these metallic ions varies

among regional samples, but frequently includes 2+ and 2+ , as these are two of the

most prevalent alkaline earth metals1 .

The significance of water hardness is prevalent in many fields of life as water is a

common natural resource. Detergent and soap-making companies take into consideration

water hardness, as hard water is highly reactive with the fatty-acids of soap, causing the

formation of undesirable gray substance, coined scum. Consequently, detergent and

soap-making companies must design products that are less reactive to these metal cations

among common water hardness 2 . In addition, industrial factories that incorporate boilers

must be aware of water hardness in an effort to avoid the clogging of pipes and jets from

metallic residue left during evaporation processes1 .

For these reasons, the necessity for water softening is a prevalent element of

industrial services. A common method utilized for this process is cation exchange resin,

which entails the funneling of hard water through columns containing resin beads of

monovalent cations (specifically + ), which replaces the divalent cations 3 . This

ultimately produces softer water.


The concentration of these metallic cations presence in water is commonly

measured in units of grains per gallon, or ppm (parts per million), most commonly of

CaCO3 . These varying degrees of water hardness are often systematized through 5

primary categories: soft, slightly hard, moderately hard, hard, and very hard4 . Scientists

frequently utilize the methods of TDS, EDTA and AA analysis to categorize water


Perhaps the simplest method, TDS, or total dissolved solids method, as inferred

from its name, simply entails the evaporation of water and analysis of residue left behind.

This process is solely qualititative analysis. Any residue is categorized as remnants of the

polyvalent cations mentioned above. For obvious reasons, this method is highly generic

and fails to provide a precise estimation of water hardness.

EDTA utilizes the compound, ethylenediaminetetracetic acid, to perform a

titration with water sample. By first adding an acid-base indicator (EBT) to the water, a

light blue color will appear, confirming a high pH of basic degree. Next, the magnesium

(2+ ) ions within the sample will react with the indicator, causing the formation of

reddish tinted solution. Through the gradual addition of the titrant,

ethylenediaminetetracetic acid, the solution will turn colorless as the EDTA reacts with

first the 2+ ions then the 2+ ions. A sudden final change in color of the solution

from red to blue will indicate the conclusion of the titration1 . By using an EDTA solution

of accepted concentration, one can easily calculate the calcium and magnesium ion

concentrations using the formula 1 1=2 2. Below is the formula for this reaction as

provided by PSU Chemtrek1 :


2 2+ 2+ + 2+
+ + + + CaEDTA + MgEDTA +

Atomic Absorption spectroscopy, or AA method, entails the usage of a

sophisticated atomic absorption spectrophotometer to gauge light absorbance. This

process is conducted by burning a small liquid sample by the machine, which then

atomizes the water sample and using a cathode lamp, passes light through the sample and

calculates the light absorbance. A specific ion(2+ + 2+ ) is focused on for each

absorbance value. By comparing the light absorbance of samples of known

concentrations, a calibration graph can be erected to create a trend line that estimates

concentration values from the provided absorption values1 .

Research of the two methods provides credibility for both techniques though each

has potential drawbacks. Due to the limited number of concentrations used, the titration

method is generally less precise to the exact concentration and generally fails for low

concentrations of metal ions 5 . In comparison, AA techniques, though precise and

generally accurate, require sophisticated equipment that is more costly. Consequently,

both methods are applicable and frequently used.

In pertinence to this concept of water hardness, an experiment was designed and

conducted to analyze and compare various samples of natural water. Using TDS, AA, and

ETDA, four unique water samples were obtained and tested from diverse regions,

including tap samples from Park City, Utah (6), Mineta San Jose International Airport in

San Jose, California (7), a local house in State College, Pennsylvania, (8), and a house in

Jamison, Pennsylvania (9).


The sample from Park City, Utah is expected to possess the highest magnesium and

calcium concentrations, based upon the locations and hardness values provided by the

USGS (United States Geological Survey). In addition, sample 2 from California is

expected to possess the lowest divalent ion concentration. Samples 3 and 4 are expected

to possess similar calcium and magnesium concentrations as they originate from similar

areas of Pennsylvania, though the State College water is expected to be slightly higher,

given data from the USGS. Therefore, using EDTA and AA analysis techniques, the

samples are anticipated to rank in order of hardness (from softest to hardest) 1, 3, 4, 2

with samples 3 and 4 being roughly equivalent, as they are from similar areas.

From PSU Chemtrek: Small Scale Experiments for General Chemistry written by

Stephen Thompson and edited by Joseph T Keiser. Pages 10-1710-24

The following experiment consisted primarily of four sections: the use of TDS

method to identify residual left from sample evaporation, Atomic Absorption

Spectroscopy to calculate ion concentration from light absorption, EDTA titration to

calculate ion concentration, and water softening through ion exchange. All of the

processes used were derived from the PSU Chemtrek booklet guidelines and were

followed accordingly. The following graph identifies where each sample originated as

well as the name of the sample analyzer and specific sample type for both AA and EDTA

analysis. None of the samples were filtered, or underwent water conditioning prior to


Table 1. Sample Identification for Lab Procedure

Sample Sample Type Location of Sample Analyzer
1 Utah Tap 6 Household (Park William Beam
City, Utah)
2 7 Mineta San Jose Alicia Alli
California Tap
Airport (San Jose,
3 Local State College N. Atherton Cameron Arthur
Tap8 Household
(State College,
4 PA Ta 9 Household Kelcie Allen

To begin, analysis of the samples was conducted using evaporation techniques. A

piece of aluminum foil (4cm x 4cm) was placed on a hot plate set on low. Using

multiple pipets, a single drop of distilled water and a single drop of sample water was

place on the foil approximately 1cm apart from one another. In addition, two drops of

1103 M 2+ solution were also placed on the aluminum foil to create a secondary

reference. The drops were allowed to slowly dissolve and the residual from each sample

was analyzed.

Next, the samples were tested using Atomic Absorption spectroscopy. First

samples 1,2,3 and 4 were diluted with distilled water in a 10 mL graduated cylinder using

a 1:1 ratio. This was achieved by mixing 5mL of distilled water with 5mL of sample

water and then stirred thoroughly. Using two new pipets, each bulb was filled over

halfway with the sample water and then the samples were transferred to 24-well tray.

Using the atomic absorption spectrometer, the liquid samples were burnt from within the

tray. Each of the samples was divided into two separate samples with one being tested for

2+ absorption and the other being tested for 2+ absorption. These absorption

values were then recorded. Using the AA standard values provided, a calibration graph

was constructed for each sample by plotting light absorbance vs. metal ion concentration

into Microsoft Excel. Next, a trend line equation was generated for both 2+ and 2+ ,

which was then used to calculate the concentrations of both ions individually. These

values (in ppm) were added together to provide a final hardness estimation using this

technique. Below is a table depicting dilution factors used for each sample.

Table 2. Dilution Factors Used for AA Method

Sample Number Sample Type Dilution Factor
1 Utah Tap6 1:1
2 California Tap7 1:1
3 Local State College Tap8 1:1
4 PA Ta9 1:1

Following AA, a divalent cation analysis was conducted through EDTA titration

methods. First, an EDTA titration was conducted using a known concentration of

1103 M 2+ solution to obtain an understanding of the process. To do this, a drop of

EBT (eriochrome black T) indicator was added to 12 individual wells. A drop of

3 /4 /Mg buffer solution was also added to each well. Finally, the wells were

titrated in succession using 2104 M EDTA, as well 1 received 1 drop of solution and

each well after received an additional drop as the one prior. The well in which the color

of the solution shifted to blue represented a complete titration, or the equivalence point.

Once completed, this process was repeated using the water samples listed above. The

experiment was conducted twice and the number of drops required to complete the

titration was averaged. Below is a chart depicting the dilution factors used for each

sample during the EDTA titration.

Table 3. Dilution Factors Used for EDTA Method

Sample Number Sample Type Dilution Factor
1 Utah Tap6 1:1
2 California Tap7 1:1
3 Local State College Tap8 1:1
4 PA Ta9 None

Finally, the samples were softened through ion exchange processes. Using the

sample dilution factor from the initial EDTA method, the samples were placed into 8mL

vial. Enough monovalent cation exchange resin was then added to each vial to cover the

bottom. These vials were then shaken up for 2-3 minutes each, and the remaining liquid

from each vial was sucked up using small-drop pipets. A pH test of the liquid then

validated evidence of successful water softening. Finally, these softened samples were

again titrated again using EDTA method.

Below are the results of the TDS analysis from the evaporated water samples. The

distilled water served as a standard for clean water containing no ions while the

1103 M 2+ solution served as a reference for water containing a minimal amount of

divalent cations. As stated above in the procedure section, with the exception 1103 M

2+ solution (2 drops), a single drop of each sample was added to the aluminum foil.

Table 3. TDS Residue Observations after Evaporation

Sample Observation
Distilled Water (clean) 6 No residue
3 2+
1 M solution (reference) 6 Distinct white ring
Utah Tap 6 More residue than reference, multiple
white rings
California Tap7 Distinct white outline compared to
Local State College Tap8 Dark white ring compared to reference
PA Ta9 Slightly pronounced ring, more than

Below are the AA-operator calibration standards for 2+ and 2+ concentrations (in

ppm) along with the absorbance values at (422.7 nm). These were used to construct the

calibration curves of the 2+ and 2+ concentrations individually which were then

translated into Graph 1 and Graph 2 using Excel.

Table 4. Check Calibration Data for 2+

+ Concentration Absorbance Value Check Standard*
(in ppm) (at 422.7nm) (in ppm)
1.000 0.00623 1.29
5.00 0.03953 5.15
10.00 0.07470 10.05
25.0 0.17207 24.53
50.0 0.32333 50.40

Table 5. Check Calibration Data for 2+

+ Concentration Absorbance Value Check Standard*
(in ppm) (at 202.5 nm) (in ppm)
1.000 0.01619 1.15
5.00 0.07192 4.84
10.00 0.12869 9.67
25.0 0.30471 25.63
30.0 0.36841 30.78
* Check Standard is a standard feedback into the instrument as a sample. Ideally, it should be the same

value as the corresponding standard. This value serves as a measure of accuracy of the AA instrument.

Graph 1. Calibration Curve for 2+ Absorbance vs. Concentration at 422.7 nm

Ca 2+ Ion Concentration Calibration for

AA y = 0.0064x + 0.0064
Light Absorbance
at 422.7 nm
0 10 20 30 40 50 60
Ca 2+ Ion Concentration (ppm)

Graph 2. Calibration Curve for 2+ Absorbance vs. Concentration at 202.5 nm

Mg 2+ Ion Concentration Calibration for

y = 0.0117x + 0.0165
Light Absorbance 0.3
at 202.5 nm 0.2
0 5 10 15 20 25 30 35
Mg 2+ Ion Concentration (ppm)

Tables 6 and 7 display the AA 2+ and 2+ , absorbance values determined for each

sample. As noted prior, all samples were diluted for this measurement using a 1:1 dilution


Table 6. 2+ Absorbance Values Obtained by AA Method at 442.7 nm

Sample Sample Type + Absorbance Value


1 Utah Tap6 0.3264

2 California Tap7 0.1785

3 Local State College Tap8 0.1735

4 PA Ta9 0.0896

Table 7. 2+ Absorbance Values Obtained by AA Method at 202.5 nm

Sample Sample Type + Absorbance Value


1 Utah Tap6 0.3149

2 California Tap7 0.1433

3 Local State College Tap8 0.1582

4 PA Ta9 0.0620

Tables 8 and 9 show the calculated concentrations values of 2+ and 2+ (in ppm) in

each sample. These values were calculated using the equation of best-fit lines given

above in Graphs 1 and 2.

Table 8. Calculated 2+ Concentrations (in ppm) from Graph 1

Sample Type Calculated + Concentration

(in ppm)
Utah Tap6 100.
California Tap7 53.8
Local State College Tap8 52.2
PA Ta9 26

Table 9. Calculated 2+ Concentrations (in ppm) from Graph 2

Sample Type Calculated + Concentration
(in ppm)
Utah Tap 6
California Tap7 21.7
Local State College Tap 8
PA Ta 9

Sample Calculation for + Concentration Using Utah Ta :

1. Given Ca2+ absorbance value = 0.1658 ppm
2. Apply Ca2+ calibration equation from Graph 1 and set absorbance value
equal to y-value. Then isolate x-value. This is the Ca2+ concentration
Y= 0.0064x +0.0064
0.3264 = 0.0064x + 0.0064
(0.3264-0.0064)/(0.0064) = x
x= 50.0 ppm 2+
3. If a dilution factor was used, then multiply by a factor of 2 to account for 1:1
s ratio
(50.0 ppm) *2= 100. ppm 2+

Sample Calculation for + Concentraion Utah Ta :

1. Given Mg 2+ absorbance value = 0.3144
2. Apply Mg 2+ calibration equation from graph 2 and set absorbance value
equal to y-value. Then isolate x-value. This is Mg 2+ concentration.
Y=0.0117x + 0.0165
0.3144 = 0.0117x + 0.0165
(0.3144-0.0165)/(0.0117) = x

x= 25.5 ppm
3. If a dilution factor was used, then multiply by a factor of 2 to account for 1:1 s
p ratio
(25.5 ppm) *2= 51.0 ppm 2+

Tables 9 and 10 display the overall combined hardness of each sample in ppm

CaCO3 . These values are be calculated by converting ppm of Mg 2+ and Ca2+ (from

Table 8 and Table 9) into ppm of CaCO3 , then adding both values together.

Table 9. Overall Hardness Values of Test Samples in ppm CaCO3

Sample Hardness Value (ppm)
1 460.
2 224
3 230.
4 96.9

Calculation for Conversion o + and + to ppm Ca Using Utah Ta :

1. First, convert Ca2+ concentration to ppm CaCO3 by multiplying by ratio of the

molar mass of CaCO3 to the molar mass of Ca2+ .
(100. ppm Ca2+ ) * (100.09 g CaCO3 /1 mole CaCO3 )*(1mole Ca2+ /48.08 g
Ca2+ ) = 250.0 ppm CaCO3

2. Next, convert Mg 2+ concentration to ppm CaCO3 by multiplying by ratio of

the molar mass of CaCO3 to the molar mass of Mg 2+ .
(51.0 ppm Mg 2+ ) * (100.09 g CaCO3 /1 mole CaCO3 )*(1mole Ca2+ /24.31
g Mg 2+ ) = 210.0 ppm CaCO3

3. Finally, add the values calculated from step 1 and step 2 together to
calculate total hardness value.
250.0 ppm CaCO3 + 210.0 ppm CaCO3 = 460 ppm CaCO3

Below are the results of the EDTA titrations for both the unsoftened water samples

(Table 10) and monovalent resin treated water samples (Table 11). The dilution

factors used in each scenario are also listed. Note: the number of drops listed in each

case in an average of two trials.

Table 10. Results of EDTA Titration (Unsoftened)

Sample Drops to Achieve Concentration of Concentration of
Equivalence Ca (moles/L) Ca (ppm)
Point (Average)
Utah Tap6 7 0.0028 280
California Tap 7
3.5 0.0014 140
Local State College 4 0.0016 160
PA Ta9 2 0.0004 40

Calculation of Ca in moles/L using Utah Ta :

= 1 x 1
( )/( 1 )= 1
((2.00 4 M)(7 drops))/(1 drop) = 0.0014 M
Note: If dilution factor of 1:1 is used, multiply final molarity by 2.
(2*0.0014 M CaCO3 ) = 0.0028 M CaCO3

Calculation of Ca in ppm using Utah Ta :

(0.0028 moles CaCO3 /L)*(100g CaCO3 / 1 mole CaCO3 )*(1000mg/1 g)
= 280 mg/L CaCO3 (1mg/L= 1ppm)
= 280 ppm CaCO3

Table 11. Results of EDTA Titration after Water Softening Treatment

Sample Drops to Achieve Concentration of

Equivalence Point Ca (ppm)
Utah Tap6 4 160 ppm
California Tap7 <1 <40 ppm
Local State College Tap8 2 80 ppm
PA Ta9 <1 <20 ppm

Table 12. Comparison of AA to EDTA Water Hardness Calculations Across Samples

Sample AA Results (ppm) EDTA Results (ppm)

Utah Tap6 460. 280
California Tap7 224 140
Local State College Tap8 230. 160
PA Ta9 96.9 40


Once synthesized, the data collected for both AA and TDS methods revealed

interesting results. In regards to overall water hardness, the PA tap sample from Jamison,

Pennsylvania, possessed the lowest values. Samples 2 and 3 from California and State

College possessed similar hardness values. In support of the original hypothesis, the Park

City, Utah sample yielded the highest overall hardness values. However, the

Pennsylvania samples greatly varied in hardness value ranges, contrary to the hypothesis.

In an effort to quantify this data, Table 12 was constructed for side-by-side

comparisons of each sample and method. Contrary to expectation, the AA results

consistently failed to provide a smaller hardness value than EDTA analysis in each

sample. AA analysis is limited in scope to search for specifically Mg 2+ and Ca2+ ions in

each sample while EDTA expands the analysis of each sample to search for the presence

of other additional divalent cations, including Iron, Strontium, and Barium. However, the

results of AA testing fail to validate this logic, suggesting potential errors in the

experiment. The most probable explanation of this consistent anomaly is the potential

contamination of the EDTA solution with the given molarity of 2.00104 M. As many

students rely on using the same bottles, it is feasible to expect that contamination

occurred, which in turn generated lower than expected values. Consequently, the

EDTA data is largely invalid for analysis as clear fallacies are present within the data.

This error was not discovered during the experiment; so further testing would be required

for a more holistic conclusion.

As stated prior, EDTA analysis identifies the presence of all (in theory) divalent

cations present in each sample. To the contrary, AA only identified Mg 2+ and Ca2+ ions

present in each sample. Consequently, the AA data should be less than or equal to the

hardness values obtained through EDTA. This trend was not true for all samples, which

largely invalidates the results of the data. Theoretically, the slight variance in hardness

values between the two methods would suggests a minimal presence of additional

divalent cations in each sample, though this conclusion cannot be drawn. These could

potentially include, Iron, Strontium, and Barium, which are frequently present, yet less

common. Ultimately, these values are within the bounds of natural water, with an overall

CaCO3 hardness value of 450 ppm, creating an ideal balance for life, according to UK

Proffessor, William Wurt10 .

Penn States A Quick Guide to Groundwater in Pennsylvania, identifies the

State College region as an area possessing very hard water potentially greater than

250ppm. This assertion can be justified by the existence of a carbonate rock aquifer

located beneath the Centre County area11 .This notion is supported by the data provided

by the EDTA and AA titrations of the PSU sample given the value of 230 ppm. The

United States Geological Survey (USGS) identifies the states of northern California and

Pennsylvania (outside of Centre County) for possessing CaCO3 concentrations in water of

121-180ppm and 60-121ppm, respectively12 . This data roughly aligns with the results of

AA for the PA Tap9 (96.9 ppm) and California tap7 (220 ppm), given a variance of 40

ppm. In addition, precipitation runoff can be attributed to increased water hardness in

areas possessing mountain ranges like that of San Jose, California, where rain water runs

down mountains and mixes with rivers, causing increased divalent ion

concentrations12,13 . This justifies the slightly higher than anticipated concentrations from

the California tap7 .

In comparison to the other methods, TDS would be the least accurate as it is based

solely upon physical observations and generalities. However, due to the atomic

absorption spectrometers capacity to gauge absorption on an atomic level, this method is

likely the most accurate of methods. In accordance with this assessment, the check

standard values reveal accuracy in the respective divalent cation concentrations, but

suggest a lack in precision as the concentrations are rounded to the nearest ones value. In

addition, if the sample is not mixed evenly, the AA readings could lack precision. A

single trial analysis of each divalent cation concentration may have facilitated a lack of

precision, in comparison to the usage of multiple AA readings to create an average

absorption value. Similarly, the EDTA method is more precise than accurate. The lack of

measurement specificity in a drop, used to quantify volume, sacrifices accuracy in

assessing the overall water hardness of each sample. However, when repeated

consistently, the titration methods as well as pipettes used should yield consistent relative

data. If a more specific unit of volume were used, rather than the whole number unit of

drop, the EDTA process would yield more accurate data.

Furthermore, during the procedure of EDTA, the equivalence point was achieved

with 7 drops in both trials, suggesting relative precision. This could be further tested with

multiple trials, though two consistent trials do provide evidence of precision. However,

particular consideration for the variance of a single drop in regards to calculations should

be accounted for as well. An increase by a factor of a single drop during the titration

yields a change in overall concentration by 40 ppm when diluted, or 20 ppm when

undiluted. This being recognized, none of the samples varied in number of drops

throughout two trials. In regards to accuracy, the titration of known concentrations of

3 M 2+ solution prior to sample testing provided insight into the methods used. With

respective percent errors of 0% and 20% for this section, Section C in PSU Chemtre1

provided credibility to the practicality and accuracy of EDTA as used in this section. This

process suggests a potential error of approximately 20% for data using this method,

which translates to a 20% error when calculating water hardness among samples.

However, in reference with the AA results, the EDTA results suggest greater error.

The accuracy of AA data can be easily calculated through percent error between

the check standard values and divalent ion concentrations provided in Table 4 and Table
5. By plugging the values from the tables into the formula: %error=
100 ,

the percent errors for Table 4 (Ca2+ Concentrations) are 29%, 3.0%, 0.5%, 1.9%, and

0.8% in order of increasing concentration. In the same order, the Mg 2+ percent errors

from Table 5 are 15%, 3.2%, 3.3%, 2.5%, and 2.6%. From these values, one can

conclude that AA is generally more accurate than EDTA, as all but one of these values is

less than 20%. In addition, the AA values generally agree more with outside data

provided, such as the USG 12 .



In an effort to analyze water hardness variations, four samples were gathered,

including Park City, Utah (6), Mineta San Jose International Airport in San Jose,

California (7), a local house in State College, Pennsylvania, (8), and a house in Jamison,

Pennsylvania (9). It was hypothesized that the Utah sample would possess the highest

hardness values while the two PA samples would produce roughly equivalent hardness

values, and the California sample would possess the lowest values.

Through total dissolved solids (TDS) analysis, atomic absorption (AA)

spectroscopy, and EDTA titration, the overall hardness values were calculated and

assessed. The experimental steps used were a direct following of the PSU Chemtrek

booklet. While the TDS yielded very similar qualitative data, the AA and EDTA methods

largely invalidated the hypothesis, but failed to fall within similar ranges. Ultimately, the

Utah sample yielded the highest concentration values, while the California sample and

the State College sample came in second with the other PA sample coming last while

possessing very soft water. The likely causation of these particularly hard samples is the

carbonate rock aquifer beneath the State College area as well as the mountains of

California and Utah. The California sample yielded hardness values much higher than

anticipated, but this can likely be justified by the presence of water run-off from

mountains, where additional divalent cations are added to the water.



1. Thompson, Steven and Jospeh T. Keiser. PSU Chemtrek: Small Scale

Experiments for General Chemistry.Hayden McNeil Publishing.
Plymouth, MI, 2015.

2. State University. Chemistry of Natural Waters.

Unknown. Web. April 16. 2017

3. Hard Water. Unknown. Web. April 16. 2017.

4. Water Quality Organization; Frequently Asked Questions.

Unknown. Web. April 16, 2017

5. Atomic Absorption Spectrophotometric and

Ethylenediaminetetraacetate-Titration Methods for Calcium and
Magnesium Determinations James Lee. Web. April 16, 2017.

6. Beam, William Experiment 10:Chemistry of Natural Waters Lab

Notebook. Pennsylvania State University. University Park. April 16, 2017
7. Ali, Alicia Experiment 10: Chemistry of Natural Waters Lab
Notebook. Pennsylvania State University. University Park. April 16, 2017

8. Arthur, Cameron Experiment 10: Chemistry of Natural Waters Lab

Notebook. Pennsylvania State University. University Park. April 16, 2017

9. Allen, Kelcie Experiment 10: Chemistry of Natural Waters Lab

Notebook. Pennsylvania State University. University Park. April 16, 2017

10. Professor William Wurt, PHD. Understanding Water Hardness Web. April
4, 2017

11. A Quick Guide to Groundwater in Pennsylvania The Pennsylvania State

University. Web. April 4, 2017

12. Water Hardness. The United States Geological Survey. Web. April 4, 2017

13. Newton, David, E. Encyclopedia of Water. Westport, Conn:Greenwood

hhhPress, 2003. Print