A Chemical Profile of

the First Mining Spoils

Lake in Alabama

Number Six Lake

Franklin County, AL

by

Mitchell Luckie

Chelsea HuneycuttCHEM 385/485

Spring 2015

Determination of Iron in Number Six Lake Water

Number Six Lake-Franklin County, Russellville, AL

Research FocusChemical and Biochemical Analysis

○ Fe in lake water

○ Percentage Fe in ore

○ Number & kinds of

mussels in lake

○ Types of carotenoids in flora and

fauna at lake

○ DNA analysis of beaver colonies

○ Percentage Ca in mussel shells

as a function of mussel species

Research FocusChemical and Biochemical Analysis

○ Fe in lake water (Murphy et al.)

○ Percentage Fe in ore (Chem 485)

○ Number & kinds of mussels in lake (Chem 485)

○ Percentage Ca in mussel shells as a function of mussel species (Chem 485)

○ Types of carotenoids in flora and

fauna at lake

○ DNA analysis of beaver colonies

HISTORY of NUMBER SIX LAKERussellville, AL

Franklin County

FACTS ABOUT LAKE:

• Mining spoils lake

• 68 acres

• Was a water reservoir for city until 1995

when Murphys bought it

• Located at first iron mine in the state

• High % Fe reported in ore

• Mine operated from 1918-1942

• Employed more than 100 people

• Furnace on site

“Shipment of the First Iron

Produced in Russellville", Mural

at Russellville Post Office, 1938

Project type: Art, Mural

New Deal Agencies: Treasury Section of Fine Arts

Completed: 1938

Artists: Conrad A. Albrizzio

○ A Section of Fine Arts fresco entitled “Shipment of the First

Iron Produced in Russellville” was painted for the Russellville,

Alabama post office in 1938 by Conrad A. Albrizzio.

○ The mural for Russellville turned out to be one of the most

controversial in Alabama. Albrizzio submitted two sketches of

local industry shortly after he was invited to undertake the

commission. The Section office chose the scene of a local

quarry over that of an early iron mine. The Section apparently

made their decision in early July 1937 and by the end of the

month they had received numerous telegrams in protest from

Russellville clubs and business concerns.

The local population proposed a slightly different theme of the old Alabama Iron

Works, the first iron furnace in Alabama, built in 1817. Similar letters were also

sent from Alabama to Senator John H. Bankhead, Jr., in Washington. One of the

letters described the general theme and the details the Russellville businessmen

wished to have included: “We know the beehive shape of all charcoal furnaces

erected at the date. We know that the furnace and forge were motivated by water

power through a race that still exists. We know they used a five hundred pound

hammer to shape the pig–we have the hammer. We know the ore was collected

by slave labor and hauled in ox carts to the furnace. We know the pig iron, much

of it, was hauled by ox wagon thirty-five miles to the Tennessee River and

shipped to Liverpool, England, and we have the records where it was sold at one

hundred dollars a ton. The rock wall foundation of the warehouse still stands

along the creek bank.” After a series of letters between Albrizzio, Bankhead, the

citizens of Russellville, and the Section, Albrizzio redesigned to the wishes of

the local population and eventually went to Russellville and painted the mural in

fresco on the walls of the post office.

Fe Analysis of Water at

Number Six Lake

Fe Analysis Method

Sampling

Grid made of lake

Samples taken at 12 different locations around lake

Samples taken from 1-25 feet depth in lake center (M)

Analysis

SCN- added to samples, Absorbance measured at 490

nm for [Fe(SCN)]2+ determination

Determine Fe concentration from calibration curve made

with standard solutions

PREVIOUS WORK

Fe concentration

in lake as function

of depth of water

A B C D E

F G H I J

K L M N O

P Q R S T

U V W X Y

Colorimetric Complex Formed

Fe(III) + SCN- ↔ [Fe(SCN)]2+

In sample excess thiocyanate iron(III) thiocyanate

Deep orange-red

Absorbs at 490 nm

Fe Analysis of Lake

Water

Calibration curve for Fe concentration

Fe Analysis of Lake Water

Percentage of Calcium in Mussel Shells

as a Function of Mussel Species

RESEARCH DESIGN

• Literature search on topic

• Why calcium measurements?

• Sample collection from Number Six Lake

• Classification of mussel shells

• Physical measurements, photographs of mussel shells

• Grinding of shells/sample preparation

• Selection of method for analysis of calcium in shells

• Ca Analysis

• Data mining, statistics, error analysis

• Conclusions

Calcium Analysis of

Mussel Shells from

Lake Number Six

Ca Analysis in Mussels from

Number Six Lake

The Collector of Mussels

At Number Six Lake

Mink (genus Mustela), either of two species of the

weasel family (Mustelidea) native to the Northern

Hemisphere. The European mink (Mustela

lutreola) and the American mink (M. vison) are

both valued for their luxurious fur. The American

mink is one of the pillars of the fur industry and is

raised in captivity throughout the world. In the

wild, mink are small, discreet, and most often

nocturnal, and they live in close proximity to

water.

Alabama rivers and waterways are home to the largest

and most diverse population of freshwater mussel

species in the nation, roughly 60% of U.S. mussel fauna.

The Mobile River Basin, which drains portions of

Tennessee, Georgia, and Mississippi waterways, also

contains diverse mussel populations. However, many of

these species have been significantly depleted in the last

century due to habitat alteration (river damming,

channelization, siltation), pollution, and invasive species,

and many more are in imminent danger of extinction.

The authors offer encyclopedic entries on each of the 178

mussel species currently identified in Alabama and the

Mobile River Basin—the scientific and common names; a

morphological description as well as color photographs of

the shell appearance; analysis of the soft anatomy;

information about ecology, biology, and conservation

status; and a color distribution map.

IDENTIFICATION OF MUSSELS

Identification of umbo

location, shell margins, and

shell characteristics. Used

reference text to classify

mussel shells.

SAMPLES OF MUSSEL SHELLS COLLECTED FROM NUMBER SIX LAKE

Six (6) Different Species Represented Here

A- Elliptio nigella B-Epioblasma haysiana C-Alasmidonta mccordi

D- Elliptio mcmichaeli E-Ellipsaria lineolata F-Elliptio crassidens

A

D

F

B

C

E

CLASSIFICATION OF MUSSELS USED IN OUR STUDY

(includes picture and scientific name)

A- Elliptio nigella

This analysis will be done volumetrically by using a

characteristic reaction of carbonate compounds, namely

their reaction with acids. Calcium carbonate (limestone) is

very insoluble in pure water but will readily dissolve in acid

according to the reaction:

2HCl (aq) + CaCO3(s) ----> Ca2+ (aq) + CO2(g) + H2O + 2Cl- (aq)

This reaction cannot be used directly to titrate the

CaCO3 because it is very slow when the reaction is

close to the endpoint. Instead the determination is

achieved by adding an excess of acid to dissolve all

of the CaCO3 and then titrating the remaining H3O+

with NaOH solution to determine the amount of acid

which has not reacted with the calcium carbonate.

The difference between amount of the acid (HCl)

initially added and the amount left over after the

reaction is equal to the amount used by the CaCO3.

The reaction used to determine the leftover acid is

HCl (aq) + NaOH (aq) ----> H2O + Na+(aq) + Cl- (aq)

1. Accurately weigh between 0.450 and 0.550 g of dried shell into each of 3

labeled 125 ml conical flasks. Be certain you record the mass of shell for

each flask in your notebook. Add several drops of ethanol to each flask.

This acts as a wetting agent and helps the HCl dissolve the CaC03.

2. Slowly pipet 10.00 ml of 1.0 M HCl solution into each flask. Swirl the flask

to wet all of the solid. Any excess HCl should be disposed of in the sink by

diluting with water. Heat the solutions in the flasks until they begin to boil

and allow to cool. Rinse the walls of the flask with water from your wash

bottle.

3. Add 3-4 drops of phenolphthalein to each flask. Using a funnel, partly fill a

clean buret with 0.100 M NaOH solution to rinse it. Empty the buret into the

sink. Fill the buret with the NaOH solution. Run some solution out to

remove all bubbles from the tip. Replenish the solution in the buret if

necessary. Read and record the initial volume to +/- 0.01 ml.

4. Titrate one sample to the first persistent pink color. When you are close to

the endpoint the color will fade slowly. Add the remaining NaOH dropwise

until the color remains for at least 30 sec. Read and record the final volume

to + 0.01 ml.

5. Repeat the titration for the other two samples.

6. Calculate the percent calcium carbonate in each sample and the mean

value. Calculate the average deviation from the mean.

CALCULATIONS

1. Calculate the number of moles of HCl added to each shell sample. This is

given by the expression:

moles HCl = (0.01000 l HCl)*(1.00 moles HCl/liter) = 1.00x10-2 moles HCl

2. Calculate the moles of HCl left in each sample after the reaction with CaC03.

moles HCl left = (vol. of NaOH in liters)*(concentration of NaOH in

moles/liter)*(1 mole HCl/1 mole NaOH)

3. For each sample determine the number of moles of HCl that has reacted

with CaCO3 by taking the difference between the moles of HCl added and the

moles of HCl remaining after the reaction is complete.

4. The moles of CaCO3 in each sample is calculated by: moles CaCO3 =

(moles HCl)*(1 mole CaCO3 / 2 moles HCl)

5. Calculate the percent CaCO3 in each sample by using % CaCO3 = [(moles

CaCO3) *(100.09 g CaCO3/mole CaCO3)*(100)] / grams of sample

6. Calculate the mean value and the average deviation from the mean.

RESULTS-Sample Calculations1) Moles HCl added = .010 L x 0.100 M HCl

=.001 moles HCl

2) Moles NaOH delivered = ____ L x 0.1011M NaOH = moles NaOH

Sample #1: 0.000157 moles NaOH

Sample #2: 0.000415 moles NaOH

Sample #3: 0.000374 moles NaOH

3) 1 - 2 = moles HCl reacted with shell

Sample #1: 0.000843 moles

Sample #2: 0.000585 moles

Sample #3: 0.000626 moles

4) Moles HCl react x (1 mole CaCO3/2 moles HCl) x 100.015g CaCO3/1 mole CaCO3

Sample #1: 0.04216 g CaCO3

Sample #2: 0.02925 g CaCO3

Sample #3: 0.03130 g CaCO3

5) % CaCO3= (g CaCO3/ g shell) x 100

Sample #1: 8.53 %

Sample #2: 5.96 %

Sample #3: 6.19 %

Mean: 6.89 Variance Standard Deviation: 1.35

Standard Deviation: 1.16

d

DATA ANALYSIS

% Ca in our samples

○ Overall:

○ % Ca

○ Mean Sample #1: 8.53%

○ Mean Sample #2: 5.96%

○ Mean Sample #3: 6.19%

○ Mean % Ca of all samples(9)= 6.89%

○ Std. Dev.= 1.16

○ Variance= 1.35

Calculations done by hand.

CONCLUSIONS○ Classification of

mussels found in

Number Six Lake (list

names of those found)

○ Ca concentration

(mean) of each species

of mussel found

Ca Analysis in Mussels

from Number Six Lake

We have used reference materials to

classify six species of mussels found in

Number Six Lake in Franklin County,

AL in the Tennessee River /Bear Creek

Watershed. These are:

Elliptio nigella

Epioblasma haysiana

Alasmidonta mccordi

Elliptio mcmichaeli

Ellipsaria lineolata

Elliptio crassidens

For Elliptio nigella :

○ Mean % Ca of all samples(9)=

6.89%

○ Std. Dev.= 1.16

○ Variance= 1.35

Other groups will report % Ca in

their species of shells today.

These are the first known

measurements of % Ca in

mussels found in Alabama

waterways.

SUGGESTIONS FOR FUTURE

RESEARCH

1. Increase grinding efficiency of shells to

make powder prior to analysis. This will

increase surface area and help make

analysis more reproducible.

2. Analyze more samples and correlate %

Ca with species-specific mussels.

3. Analyze Ca content of lake water.

4. Continue with determination of %Fe in

hematatite (iron ore) found on site at

Number Six Lake.

YOUR QUESTIONS???

Ca Analysis in Mussels for

Number Six Lake