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Wastewater Treatment: The Identification of Contaminants in a Water Sample and the

Effect of Various Remediation Techniques on Water Sample Contaminant Quantity


Danling Ye
Desk #48
TA: Lisa Funari
Chemistry 113 Environmental
March 27, 2014
















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Introduction
Humans use tremendous amounts of water to run their societies. However, the
wastewater produced through human industries, agriculture, and home usage cannot be
directly reintroduced into the main water system without detrimental environmental
effects. Wastewater treatment is important because it cleans up the water before it is
introduced in the environment. The problem of wastewater is not limited to treating so it
can be introduced back into the environment however; since effluent water is higher in
temperature than normal stream water, it poses a threat to wildlife if introduced in large
qualities.
1
Thus, if wastewater can be reused in an environmentally friendly way, people
can decrease their environmental footprint. Reusing water poses several challenges.
Firstly, water must be treated extremely well; it must be cleaner than drinking water
before leaving the treatment plant.
1
Water released into the environment can have more
contaminants than water for reuse, making water for reuse harder to produce. Secondly,
many different types of contaminants can exist in a sample of water, so many different
types of treatments might have to be used. Wastewater treatment can also be very
expensive; for example, reverse osmosis pumps prevent contaminants from passing
through a barrier that allows water to pass.
1
They can filter water very well, making
seawater consumable. However, they are approximately $1,700.
1
In addition to treating
wastewater, treatments can be used to restore polluted bodies of water.
Several types of water pollution exist. Agriculture runoff can contain high levels
of nitrates and phosphates.
1
In addition, wastewater treatment plants can cause nitrate
pollution, and industrial and municipal wastewater discharges can contain phosphorous.
2
Both nitrate and phosphorous are limiting nutrients needed for plant growth. When
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pollution increases the amount of phosphorous and nitrates found in the water, algae
growth increases dramatically; the eutrophication causes oxygen depletion, which
damages the ecosystem by making it harder for organisms to survive.
2
In the future,
nitrate and phosphate pollution will become an even bigger problem; global population is
expected to double from 2002 to 2050, drastically increasing the demand for agricultural
products.
3
In addition, as standards of living increase, the demand for meat products also
increases; per pound of product produced, the production of meat causes more pollution
than the production of crops, making it even more important to find solutions to remedy
agriculture pollution.
3
Another type of pollution is heavy metal pollution. Factories and
industry can release many heavy metal pollutants.
1
Organic contaminants can also cause
pollution and come from pesticides, herbicides, gasoline, roadwork, and other human
activity residues.
1
Many organic compounds are regulated for drinking water, and they
can cause disease or death in animals. Hard water also needs remediation before human
use. Hard water is usually caused by calcium and magnesium ions, though other cations
can contribute to hardness. Calcium and magnesium are usually added naturally to bodies
of water because groundwater passing through soil and rock will pick up the elements;
however, drainage from mine sites, wastewater from homes, and industrial discharges
may also cause hard water.
1
Another common type of pollution is acidic pollution. Acid
mine drainage pollutes almost half of Pennsylvanias polluted waters.
4
It occurs when
water enters coal mines mostly abandoned coal mines and reacts with iron pyrite in
the coal and rocks to form acid that runs off into streams and rivers.
4
Acid rain is caused
by SO
2
and NO
x
from fossil fuel power plants, industry, car exhaust, and other sources.
1

Acid mine drainage and acid rain both causes a lowering of pH. Fish and other aquatic
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life survive optimally at a certain pH range, and a pH lower than 5.0 causes water to be
uninhabitable for most organisms.
1

To treat wastewater or polluted bodies of water, people must first determine the
contaminants in the water sample. Several techniques are available. In the laboratory
scenario, students were given a sample of water with two contaminants; the possible
contaminants were Fe
2+
(a model for heavy-metal contamination), excess hardness
caused by Mg
2+
and Ca
2+
, an acidic species, or an organic contaminant.
1
To determine the
contaminants, students could use spectrophotometers (Spec-20), atomic absorption
spectrophotometry, and pH paper.
1
In the Spec-20, light of a certain wavelength passes
through a sample and the amount of light transmitted is measured.
1
The wavelength is set
depending on what constituent is being measured; if needed, the chemical species in
question reacts with a reagent that produces a colored compound before the sample is
analyzed.
1
From the amount of light transmitted, the amount of light absorbed can be
calculated and the concentration of the sample can be found by comparing it to the
absorbance of samples of known concentration.
1
The second technique, atomic
absorption spectrophotometry, uses the absorbance of incident light with a certain amount
of energy, depending on the atom of interest.
1
If the atoms in the sample have the same
change in energy as the energy of the incident light, the atoms will absorb the incident
light.
1
Depending on the amount of absorption, scientists can determine the quantity of a
certain metal in a sample.
1
The third technique, pH paper, involves placing litmus paper
in solution. The paper has been treated with indicators that change color depending on the
pH present in the solution. By using pH paper, the pH of a sample can be determined.
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The scientists hypothesize that they will be able to treat the contaminants present
using different techniques depending on the contaminants present. If the sample has
excess hardness, it is hypothesized that a remediation technique using resin would
decrease the hardness. If the sample has an acidic species or Fe
2+
contamination, a
limestone treatment is hypothesized to increase the alkalinity of the solution and help
remediate the problem. If the sample contains an organic contaminant, a treatment using
activated carbon is hypothesized to help remediate the sample.
Procedure
The scientists were given a sample of water with unknown contaminants, labeled
as sample #4. The samples color was observed and was not yellow; if the sample is
yellow, the atomic absorption spectrophotometer was not used in the experiment. Three
samples were prepared to be analyzed by the atomic absorption spectrophotometer. One
sample consisted of pure distilled water, the second was a 50% dilution of sample #4, and
the third sample was sample #4 diluted to a concentration of 25%. Both of the dilutions
were diluted with distilled water. Each sample was put in a pipet with the tip cut off so
that the bulb was about two-thirds full. To analyze the sample for hardness caused by
Mg
2+
and Ca
2+
, the atomic absorption spectrophotometer was used. The atomic
absorption spectrophotometer was zeroed using the distilled water sample; then the two
diluted samples were tested. Two spectrophotometers were used: one to check for Mg
2+

and one to check for Ca
2+
. The value on the atomic absorption spectrophotometer when
the sample was analyzed had to be on a given calibration graph in order to determine the
concentration of Mg
2+
or Ca
2+
originally in the sample, thus the two dilutions were tested
to see if the value of the dilution was in the range of given values on a atomic absorbance
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standard chart. The given values of absorbance corresponded to known concentrations of
the elements. The dilution factor of the sample and value on the atomic absorption
spectrophotometer were recorded for each element tested when the value for the sample
was in the range given by the standard chart. Afterwards, the concentration of the sample
was calculated by analyzing the absorbance of samples of known concentration and the
absorbance of sample #4.
Next, the spectrophotometer (Spec-20) was used to analyze the sample for Fe
2+
.
The Spec-20 was set to a wavelength of 562 nm because that is the wavelength in which
the iron absorbs light depending on its concentration. A blank was prepared using 3.000
mL of blank that was mixed with 0.1 mL of ferrozine reagent by inversion. Then 0.1 mL
of pH buffer was added to complete the blank and the solution was allowed to sit for 2
minutes, and then placed in the Spec-20. The transmittance of the Spec-20 was set to
100%. Then, the sample was prepared in the same way as the blank; the same reagents
and process was used except that the 3.000 mL of blank was replaced with 3.000 mL of
the sample. If light was absorbed and the transmittance was not 100%, further analysis
was needed. Samples with known iron concentration of 0.5 ppm, 1.0 ppm, 1.5 ppm, and
2.0 ppm are prepared one at a time in the same way as the blank; replacing the 3.000 mL
of blank with 3.000 mL of the respective sample. The transmittance for each is recorded
and the absorbance is calculated from the transmittance. Then, a plot of the known
absorbance values is generated and the absorbance of the unknown sample is calculated
using the absorbance of the known samples.
Next, the pH was determined by placing a strip of litmus paper in the sample. The
paper changes color depending on the pH of the solution and the color of the litmus paper
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can be compared to a chart depicting the color of the litmus paper at different pH to
determine the pH of the sample.
If the pH test determined that the sample was acidic, or had a pH less than 7, then
the Spec-20 was used again to test for Acid Orange 63 contamination. For Acid Orange
63, the Spec-20 is set to a wavelength of 425 nm and blanked with distilled water. Then
the sample was placed in the Spec-20 to determine if there was Acid Orange 63
contamination by looking at the transmittance. If the transmittance was not 100%, there
was contamination. If the sample had Acid Orange 63 contamination, the transmittance of
samples with known concentrations of Acid Orange 63 was determined using the Spec-20
and the absorbance was calculated from the transmittance values. Then, the concentration
of the unknown was determined using the concentration and absorbance of the known
samples.
Next, two remediation techniques were determined depending on the
contaminants present, making sure that the remediation technique used first was not
hypothesized to cause additional remediation problems that cannot be fixed using the
second method of remediation. The second remediation was done not on the original
sample, but on the sample that had been treated with the first technique. If the sample was
excessively hard, resin was used. Resin was placed at the bottom of a 20 mL screw cap
vial, covering the bottom of the vial. Then, the vial was filled with sample and heated on
a hot plate at around 275C for 20 minutes and stirred occasionally with a straw. The
sample was then filtered and reanalyzed using the atomic absorption spectrophotometer
to determine the new concentrations of Ca
2+
and Mg
2+
to determine if the remediation
technique was successful.
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If the sample had a low pH or Fe
2+
contamination, then limestone granules were
used as a remediation technique. Limestone was placed at the bottom of a vial, and then
the sample was placed on top of the limestone. It was heated with the dial at 275C on a
hot plate for around 20 minutes; the solution boils at around 100C. The solution was
stirred occasionally with a straw, then filtered. The pH was taken using litmus paper to
determine the success of the technique.
If the sample had an organic contaminant, the sample was remediated using
activated carbon in a similar fashion as the resin; instead of using resin, activated carbon
was used. To determine the success of the remediation technique, the sample was tested
using the Spec-20 to determine the concentration of the organic contaminant and whether
the sample successfully got rid of the organic contaminant. In addition, a pH test was also
used.
Since sample #4 had heavy metal contamination and a low pH, resin remediation
was used, followed by remediation by limestone granules. The sample that was diluted to
25% of the original concentration was used for the remediation process.
Results
The absorbance value of sample #4 when it was diluted to 25% was 0.1840 when
it was tested for Ca
2+
and 0.2809 when it was tested for Mg
2+
.
To calculate the concentration of the Ca
2+
and Mg
2+
in the sample, known atomic
absorption standards, as seen in Table 1 and Table 2, were used. The values were
calculated and given to the experimenters and not determined during the experiment.


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Table 1: Atomic Absorption Standards for Calcium

Calcium Concentration (ppm) Absorbance Value (at 422.7 nm)
Check Standard
(ppm)
0 0.00879 1.37
5 0.04515 4.13
10 0.07962 9.12
25 0.17777 24.44
50 0.34857 49.98


Table 2: Atomic Absorption Standards for Magnesium
Magnesium Concentration
(ppm)
Absorbance Value (at 202.5
nm)
Check Standard
(ppm)
1 0.01975 1.11
5 0.0704 5.83
10 0.11994 10.64
25 0.2868 25.82
30 0.3524 29.67

Using the line of best fit for the calibration graph for atomic absorption of Mg
2+

and Ca
2+
, the concentration of Mg
2+
and Ca
2+
in sample #4 was calculated.

y = 0.0068x + 0.0103
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 10 20 30 40 50 60
A
b
s
o
r
b
a
n
c
e

a
t

4
2
2
.
7

n
m

Concentration of Ca
2+
(ppm)
Graph 1: Calibration Graph for Atomic
Absorption Analysis of Calcium
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To determine the Ca
2+
or Mg
2+
in sample #4, two points on the line of best fit
were chosen to determine the slope of the line. During the lab experiment, the
experimenters estimated the line of best fit and choose two points they believed to be on
the line to calculate the line of best fit. To analyze Ca
2+
contamination, calculations were
done as follows: two points, (x
1
, y
1
) and (x
2
, y
2
) were chosen, where x
1
was a
concentration of Ca
2+
and y
1
was the absorbance value on the line of best fit
corresponding to the x
1
value chosen. (x
2
, y
2
) was another point chosen in the same
manner. Let (x
1
, y
1
) = (20.0, 0.15) and (x
2
, y
2
) = (12.5, 0.1). To calculate the slope of the
line, denoted as m, use the equation m = (y
1
-y
2
)/(x
1
-x
2
). m = (y
1
-y
2
)/(x
1
-x
2
) = (0.15-
0.1)/(20.0-12.5) = 0.006667 (absorbance value at 422.7 nm)/(concentration of Ca
2+
in
ppm). The equation for a line in slope-intercept form is y = mx + b, where b is the y-
intercept. To calculate b, solve the equation y = mx + b for b to obtain b = y - mx. Since
m was calculated, it can be plugged into the equation. To determine b, use a point on the
line of best fit, (x
1
, y
1
) and solve b = y
1
- mx
1
. b = 0.15 - (0.006667)(20.0) = 0.01667
(absorbance value at 422.7 nm). Thus the equation of the line of best fit is y = 0.00667x +
y = 0.0113x + 0.0096
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 5 10 15 20 25 30 35 A
b
s
o
r
b
a
n
c
e

V
a
l
u
e

a
t

2
0
2
.
5

n
m

Concentration of Mg
2+
(ppm)
Graph 2: Calibration Graph for Atomic
Absorption Analysis of Magnesium
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0.01667. To find the concentration of Ca
2+
of sample #4, solve for x given the known y =
0.1840. Since the sample was diluted to 25%, multiply the x found by 4 to obtain the
concentration of the original sample.
x = (y-0.01667)/(0.00667) = (0.1840-0.01667)/(0.00667) = 25.087 ppm. The original
concentration of Ca
2+
in sample #4 is 4 x 25.087 ppm = 100.348 ppm.
To analyze for Mg
2+
contamination, calculations were done in the same matter as
the calculations to determine Ca
2+
contamination. The equation for the line of best fit for
Mg
2+
contamination was y = 0.01257x + 0.005725, and the concentration of Mg
2+
in the
original sample was 87.5656 ppm. The total hardness of the water was found by adding
the concentrations of Ca
2+
and Mg
2+
and was 187.914 mg/L CaCO
3
.
When the sample was tested for Fe
2+
contamination using the Spec-20 as outlined
in the procedure, it was determined that there was 100% transmittance and thus no
contamination.
When the sample was tested with pH paper, the paper was pink, indicating a very
acidic pH of 2.
When the Spec-20 was used at a wavelength of 425 nm as outlined in the
procedure to test for Acid Orange Contamination, the transmittance was 100%, indicating
that there was no Acid Orange Contamination.
After the 25% concentrated sample was remediated using resin, the reading for
Ca
2+
was 0.0019 (y = 0.0019) and the reading for Mg
2+
was 0 (y = 0) according to the
atomic absorption spectrophotometers. Solving for the x value of concentration using the
respective equations found previously, and multiplying the value by 4 to account for the
dilution, the final concentration of Ca
2+
was -2.2144 ppm and the final concentration of
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Mg
2+
was -1.8218 ppm. After resin remediation, limestone remediation was used and the
pH was taken. The Litmus paper was green, indicating a pH of 7.
Discussion
The original concentration of Ca
2+
in sample #4 as obtained by the atomic
absorption spectrophotometer was 100.348 ppm and the original concentration of Mg
2+
in
the sample was 87.5656 ppm. The total hardness of the water sample was 187.914 mg/L
CaCO
3
. The sample water was hard because water samples with greater than 180 mg/L
CaCO
3
are classified as very hard.
5
In addition, the scientists had to dilute the sample to a
25% concentrated sample for it to fall on atomic absorbance standard chart, indicating
that there was Mg
2+
and Ca
2+
contamination in the sample. The values obtained for
hardness and concentration of Ca
2+
and Mg
2+
for one scientist was different then those
obtained by the scientists lab partner because both individuals drew their own line of
best fit for the graph.
6
However, both scientists obtained values that indicated the sample
was hard.
6
In addition, the true line of best fit, as seen on Graph 1 and Graph 2 and
calculated using the computer, was different than the one obtained by the scientists, and
thus Ca
2+
and Mg
2+
concentrations and hardness values obtained using that line of best fit
would be different than that obtained by the scientist. Thus the calculated value for
hardness, Ca
2+
concentration, and Mg
2+
concentration might differ slightly from the
actual value because of errors when the scientist found the line of best fit for the atomic
absorption analysis of Ca
2+
and Mg
2+
concentration. In addition, only two diluted
samples, a 50% concentrated sample and a 25% concentrated sample were tested for each
element, and only the 25% concentrated sample had a value that could be analyzed using
the known values. The small sample size of one meant that there was a high likelihood
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that the sample was unusual just by chance; a larger sample size usually increases the
precision of the data.
7
Though sample #4 seemed to be a homogenous solution, it is
possible that it was not and the sample taken to be analyzed was not representative of the
sample as a whole, introducing possible error. Since the real concentration of heavy metal
contaminants in the sample was not known, the accuracy of the data could be not
accessed. However, the atomic absorption spectrophotometer was calibrated and check
standards were determined by researchers as a step to ensure accuracy of the data
obtained in the experiment.
When the sample was tested for Fe
2+
contamination using the Spec-20 as outlined
in the procedure, it was determined that there was 100% transmittance and thus no
contamination. However, when the sample was tested with pH paper, the paper was pink,
indicating a very acidic pH of 2 and presence of an acidic contaminant. Since the
contaminants in the sample were not known by the experimenters but known by those
that prepared the samples, the experiments learned that there was Fe
2+
contamination in
the sample that caused the low pH. However, since they originally did not know that
there was Fe
2+
contamination, they did not calculate a Fe
2+
concentration value of the
original sample or remediated sample. There are many possible sources of error that
prevented the experimenters from detecting the Fe
2+
in the sample. First of all, sample #4
was only analyzed one time for Fe
2+
contamination before the researchers concluded that
there was no Fe
2+
contamination. It is possible that the sample taken for the analysis was
not representative of the sample as a whole and did not contain Fe
2+
contamination. More
likely, the researchers made a mistake when following the procedure. They could have
set the Spec-20 to a wavelength that was not 562 nm or they could have added the wrong
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reagents or wrong quantities of reagents to the blank or to the sample. The researchers
had experience using the Spec-20 before, but they were still relatively inexperienced,
making experimental error likely.
When the Spec-20 was used at a wavelength of 425 nm as outlined in the
procedure to test for Acid Orange Contamination, the transmittance was 100%, indicating
that there was no Acid Orange Contamination. The pH of 2.0 indicated that there was
acidic contamination, but as mentioned above, it was known that Fe
2+
caused the
contamination. Again, only one sample was analyzed before concluding that there was no
Acid Orange Contamination, a larger sample size could allow the scientists to calculate
precision of the data, assuming that it is possible for sample #4 to have Acid Orange
Contamination.
After the 25% concentrated sample was remediated using resin, the readings taken
using the atomic absorption spectrophotometer for Ca
2+
was 0.0019 and the reading for
Mg
2+
was 0; the final concentration of Ca
2+
was -2.2144 ppm and the final concentration
of Mg
2+
was -1.8218 ppm. When the samples were analyzed, the final samples had a
negative final concentration of Ca
2+
and Mg
2+
. It is not possible to have a negative
concentration, however since the concentrations were calculated using a line of best fit
and extrapolated data, the negative concentrations just indicate a very low final
concentration of Ca
2+
and Mg
2+
. Also, the line of best fit as determined by the scientist is
not the same as the line of best fit as determined by a computer, indicating that the
negative values could be caused because of the scientists minor inaccuracies in
determining the line of best fit. The low readings on the atomic absorption
spectrophotometer and low Mg
2+
and Ca
2+
concentrations indicate that the remediation
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technique was successful. Resin remediation allows ion exchange, in which two sodium
ions will be exchanged for one Ca
2+
or Mg
2+
ion, allowing the Ca
2+
or Mg
2+
ions to be
taken up, decreasing the hardness.
1
After resin remediation, limestone remediation was used and the litmus paper was
green, indicating a pH of 7. The increase in pH indicated that limestone remediation was
successful in increasing the pH. The limestone increased the pH because dissolved
limestone adds CaCO
3
to the water. The CaCO
3
can act to increase alkalinity by reacting
with H
+
ions according to the following reactions:
CO
3
2-
+ H
+
HCO
3
-

HCO
3
-
+ H
+
H
2
CO
3
.
Both of the remediation techniques were successful. However, the experimenters
used the 25% concentrated diluted sample for the remediation, while they were supposed
to remediate the undiluted sample. If the undiluted sample was remediated, the
techniques used might have been less successful because the concentration of
contaminants in the original sample would have been greater than the concentration of
contaminants in the diluted sample.
The source of sample #4 was probably near an area of heavy industry or
urbanization. Factories and industries can release heavy metals that end up in the water.
1

In addition, wastewater from homes can contain some heavy metals.
1
Acid rain is caused
by SO
2
and NO
x
from sources related to industry or urbanization such as fossil fuel
power plants, industry, and car exhaust.
1

For the experiment, the scientists remediated a small sample. For the remediation
techniques to be successful on a large scale, other factors must be taken into account. In
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the experiment, resin was used to decrease hardness, and then limestone was used to
increase pH. Using limestone increases the hardness of a sample; thus if resin and
limestone are used in conjunction as a remediation technique, limestone has to be used
before resin. However, using limestone before resin might prove impractical or
problematic. In addition, a remediation technique must be cost efficient on a large scale
and applicable to a large amount of water. Limestone might be a cost effective technique
because it is simple, relatively inexpensive, and requires little maintenance when applied
to a large area.
1
However, it has its drawbacks. It might not be effective over a large
period of time and results of limestone remediation are inconsistent.
8
In addition, dosage
recommendations for limestone use are not well-defined, which could lead to wasted
money if more limestone is applied than needed, or no drastic change in pH if too less
limestone is applied.
8
Resin might not be practical on a large scale because it is
expensive.
1
In addition, iron-exchange resins must be regenerated for the resins to
function well.
9
However, other techniques, such as boiling water, might be used to
decrease hardness.
1
In addition, biological remediation techniques can be used reduce the
use of chemicals.
1

Conclusion
Wastewater is produced through many aspects of human activity. It cannot be
released back into the environment without having detrimental effects on the
environment, thus it is necessary to clean wastewater. In addition, wastewater treatment
that allows water to be reused can help people decrease their environmental footprint.
Several types of water pollution commonly occur. Agriculture runoff can contain
high levels of nitrates and phosphates.
1
Wastewater treatment plants release nitrates into
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the environment, and industrial and municipal wastewater discharges release
phosphorous.
2
Factories and industry release many heavy metal pollutants into the water
supply.
1
Organic contaminants can come from pesticides, herbicides, gasoline, roadwork,
and other human activity residues.
1
Acid mine drainage and SO
2
and NO
x
from fossil fuel
power plants, industry, car exhaust, and other sources cause a lowering of pH, which can
have many detrimental effects to aquatic life.
1

To treat wastewater or polluted bodies of water, people must first determine the
contaminants in the sample. In the laboratory scenario, students used spectrophotometers
(spec-20), atomic absorption spectrophotometry, and pH paper to determine contaminants
in a sample.
1
The experimenters hypothesized that different remediation techniques could
be used depending on the contaminant. If the sample had excess hardness, it was
hypothesized that a resin remediation technique would decrease the hardness. If the
sample had an acidic species or Fe
2+
contamination, it was hypothesized that a limestone
treatment would increase the pH. If the sample contained an organic contaminant, it was
hypothesized that a treatment using activated carbon would help remediate the sample.
After conducting the experiment, the scientists concluded that sample #4 had
heavy metal contamination and a low pH. Resin remediation was used, followed by
remediation by limestone granules. The remediation techniques were successful in
decreasing heavy metal contamination and increasing pH. However, the scientists were
told that their sample had Fe
2+
contamination, which they did not detect. Possible human
error and the low sample size might have decreased the validity of the results. Based on
the contaminants present in the sample, sample #4 probably was obtained near an area of
heavy industry or urbanization.
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Remediation of wastewater on a large scale has several challenges. Cost and
practicality on a large scale must be taken into account. Techniques such as limestone
remediation, resin remediation, boiling water, and biological remediation techniques may
be used to treat wastewater; however, they all have their own drawbacks.



















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2+
], Alkalinity, and Metal Ion Content of Local Water
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#B14
2) "Water Quality." Water Quality. Center for Earth and Environmental Science Indiana
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