Determination of the Cause of a Fish-Kill in the

Clark Fork of the Columbia River

Write Up















Kristina Hanks

Introduction
In 1984 a major fish-kill occurred in the Clark Fork of the Columbia River. Each partnership of
students will be analyzing a simulated water sample from the river to determine the presence of
Na
+
, K
+
, Li
+
, Ca
2+
, Ba
2+
, Sr
2+
, Cu
2+
, and Fe
3+
. The evaluation of the water sample will determine if
the water has too high of a salinity by reporting any toxic levels of Cu
2+
and Fe
3+
.
What is responsible for the fish-kill in the Clark Fork of the Columbia River?
There will be utilization of knowledge gained from previous experiments such as absorption
spectroscopy and emission analysis.
To use emission analysis to determine Na
+
, K
+
, Li
+
, Ca
2+
, Ba
2+
, and Sr
2+
we have to know
the energy, E, of the emitted light is the product of Plancks constant, h = 6.63 x 10
-34
Js, and
the frequency of light, v.
E = hv
With this equation we can determine the relationship between the energy and wavelength.
v = c/
E = hc/
Using previously known standards from the emissions lab we can determine the presence of
these spectator ions by the wavelength intensities presented on the emissions reading.
Students may discover toxic levels of Cu
2+
and Fe
3+
and determine this as the cause for
the massive fish-kill. They must figure out the concentration of these two metal ions using
absorption spectroscopy. The concentration range for the standard solutions used to
determine the concentrations of Cu
2+
and Fe
3+
is 400 ppm to 50 ppm.

Experimental Procedure

Emission Analysis
Each team will analyze the water sample to determine the presence of spectator ions Na
+
, K
+
,
Li
+
, Ca
2+
, Ba
2+
, and Sr
2+
using the Spectrometer. They will compare the trials of testing water to
previously known wavelengths from the previous Emissions Lab.
For testing the unknown water sample
1. See Appendix E- Instructions for Recording an Emission Spectrum Using the
MeasureNet Spectrophotometer complete Steps 1-7 in Appendix E before continuing
to Step 2
Press the On button to activate the station. Then press Main Menu, the press
F5 Spectroscopy, then press F1 Emission.
Press SetUp to establish measurement limits. Press F1 and use the arrow
keys to navigate the menu. Set the Y-axis (intensity) with a min of 0 and a max of
1500. Leave the X-axis (wavelength) on its default settings, then press Display.
2. Obtain ~1 mL of the unknown water sample and a nichrome wire. Record the unknown
number in the lab report.
3. Clean the nichrome wire by placing 5 mL of 6 M HCl in a 50-mL beaker. Dip the nichrome
wire into the 6 M HCl and swish the wire in the solution for 30-40 seconds to insure that
it is thoroughly clean
4. Rinse the wire with 30-50 mL of distilled water. Pour the used acid into the Waste
Container.
5. See Appendix E- Recording an Emission Spectrum. Complete Steps 8-24 in Appendix E
before proceeding to Step 6.
6. After the lab, use Microsoft Excel to construct emission spectra graphs and compare
the sample data to the data of the Group IA and IIA metals obtained from the emission
lab first semester. Using Formula One below, determine the energy emitted per mole at
the two greatest peaks and compare these numbers to the energy at peaks of known
metal ions obtained in a previous experiment.
7. Prepare an XY Scatter Plot to plot the emission spectra for the unknown

Absorption Spectroscopy
Cu
2+
and Fe
3+
in chloride complexes can weakly absorb visible light. By adding thiocyanate ions to
the metal ions, highly colored complexes are formed that can absorb visible in widely separated
absorbance bands.
Teams will test concentrations of both thiocyanate complexes ranging from 400 ppm to 50
ppm using absorption spectroscopy.
1. Obtain ~20 mL of the Cu
2+
and Fe
3+
and the unknown solutions.
2. Prepare 10.00 mL of each of the five standard solutions.
a. Use the formula (M1)(V1)=(M2)(V2) to calculate the dilutions for the solutions
of [CuSCN]
+
and [FeSCN]
2+

b. Report all dilution calculations.
3. Record absorption spectra of the solutions. See Appendix D- Instructions For
Recording an Absorbance Spectrum using the MeasureNet Spectrophotometer
4. Select a
max
for the solutions
5. Fill in the data table with concentrations and corresponding absorbancies
6. Record he simulated lake water sample in the lab report
7. Prepare a Beer-Lambert Plot using the data compiled in Step 5. See Appendix B-2: Excel
Instructions for Performing Linear Regression Analysis
8. Determine the concentration for the simulated lake water sample
Thiocyanate will then be added to the water sample and that will be tested using absorption
spectroscopy and compared to the standards of the previously tested thiocyanate complexes.




Results for Unknown #4:
Emission Analysis:
From the emission spectra created during this experiment, it has been concluded that Unknown
4 contained Na
+
, K
+
, and trace amounts of Ca
2+
and Li
+
. These conclusions were drawn from
comparing the energy of the waves in the individual ions and then the energies of the
wavelengths in the ions and verified through visual comparison of graphs.

Na
+
:
E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (5.8965*10
-7
)
E= (3.37*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=202 kJ/mol
K
+
:
E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (7.6623*10
-7
)
E= (2.59*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E= 156 kJ/mol
Ca
2+
:
E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (5.5486*10
-7
)
E= (3.58*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=216 kJ/mol

E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (6.2597*10
-7
)
E= (3.18*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=191 kJ/mol
Li
+
:
E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (6.7159*10
-7
)
E= (2.96*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=178 kJ/mol
Unknown 4:
E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (5.5418*10
-7
)
E= (3.58*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=216 kJ/mol

E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (5.9033*10
-7
)
E= (3.37*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=202 kJ/mol

E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (6.2597*10
-7
)
E= (3.18*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=191 kJ/mol
E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (6.7093*10
-7
)
E= (2.96*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E=178 kJ/mol

E= ((6.63*10
-34
Js)(3.00*10
8
m/s)) / (7.6623*10
-7
)
E= (2.59*10
-19
J/atom)(1kJ/1000J)(6.02*10
23
atoms/mol)
E= 156 kJ/mol

Absorption Analysis:
During this lab we made five standard dilutions for the 0.1 M iron(III) nitrate solution, 0.1 M
copper(II) nitrate solution and the standard Fe/Cu solution containing 400 ppm Cu
2+
and 20 ppm
Fe
3+
in SCN
-
solution. The formula (M1)(V1)=(M2)(V2) was used to calculate the dilutions.

412.61 nm was the
max


Cu
2+
Cu
2+


Fe
3+
Fe
3+
Cu/Fe
Solution
Cu/Fe
Solution
Concentratio
n
Absorptio
n
Concentratio
n
Absorptio
n
Concentration Absorption
400 ppm 0.169 20 ppm 0.049 400/20 ppm 0.739
200 ppm 0.052 10 ppm 0.049 200/10 ppm 0.301
100 ppm 0.027 5 ppm 0.05 100/5 ppm 0.113
50 ppm 0.011 2.5 ppm -0.014 50/2.5 ppm 0.038
25 ppm 0.012 1.25 ppm -0.008 25/1.25 ppm 0.024
Unknown Absorption: 0.159
Concentration Cu
+
: 319 ppm
Concentration Fe
3+
: 5.06 ppm
Using the Beer-Lambert Plots created, we can determine the concentrations of the unknown
substance

Conclusion:
I believe that this experiment was very successful in determining what ions were present in the
unknown water sample, however it was somewhat difficult to determine
max
and was done
through some trial and error. However, I think it was an interesting lab over all and I believe that
we accomplished determining the ions and concentration very well.