Development and Analysis of a Double Displacement

Method to Detect Nitrates, Sulfates, and Phosphates

Tony Zheng

Abstract
Water is vital for life; thus, monitoring the health of our water is
essential. Nutrients are considered a major threat to the health of
water bodies worldwide. There are numerous methods
established to detect for nutrients; however, many of them are
extremely costly per test, qualitative, take a 2 hour period or
longer, and/or are difficult to fund for long periods of time. This
study includes the development and evaluation of a novel method
to detect nutrients. To assess the novel method, SO2, NO, and
PO3 ions were tested and compared. Forty-six water samples
were gathered from the Metedeconk River, NJ and a Brick MUA,
NJ tap water source. Samples were tested using the novel method
against a LaMotte SMART 2 Colorimeter. Results were then
compared to the Brick MUAs state lab test methods. Results
suggest that the novel method was 10 times faster, 23.48% more
accurate, and 970 times cheaper compared to the colorimeter.
Compared to the Brick MUA Lab, the novel method is 180 times
faster, with 3.83% error, 12,500 times cheaper.

Background
Without water life would not exist on Earth (Hunter et al. 2010). However,
most of the water on Earth is contaminated. Organizations like The U.S.
Environmental Protection Agency are devoted to identifying and eliminating
contaminations from water bodies. Statistics from The Pacific Institute
reports that every year over 2 million tons of sewage, agricultural, industrial,
and human waste are discharged into the worlds water. Worldwide, 2.5 billion
live without improved sanitation (Drinking Water Contaminants 2012). Water
contamination is a prevalent issue and must be dealt with.
The biggest contributors of water contamination is nutrient runoff
(nitrates, sulfates, and phosphates). In the United States, fertilizer runoff is
the cause of a 6,000 square mile death zone west of the Mississippi River and
off the coast of Louisiana (Effects of Pollution 2012). Nutrients enter a water
body and over fertilizers the organisms in the water, particularly algae. Algae
respond to this sudden outbreak of nutrients by increasing reproduction. An
outbreak of algae will deprive the system of oxygen until it becomes a dead
zone void of life in a process known as eutrophication. Constant nutrient
monitoring is essential to ensure the health of water body.

Figure 1: Process of Eutrophication

Figure 2: Dead zone distribution around the world

The most commonly used method to date to detect for nitrates, sulfates,
and phosphates is a colorimeter (What Is a Colorimeter 2012). Colorimeters
apply the Beer-Lamberts Law to detect for contaminants. Essentially, the
colorimeter beams ultraviolet light through the sample and determines the
amount of solute present based on color absorbance (What is a Colorimeter
2012). However, colorimeters utilize optics thus cracks in the vial or
crystalline solids (NaCl) will create erroneous readings. Furthermore,
colorimeters take 10 minutes to run, costly, and inaccurate. Thus, there needs
to be a more efficient method to monitor nutrients.

Monmouth Junior Science Symposium

New Jersey Monmouth Region

Objective

Laws and Principles

Beer-Lambert Law: The amount of light absorbed by a solution is proportional to the concentration of solutes in the solution.

Phase 1: Utilize stoichiometry and solubility rules to create a different approach to detect nutrients.

Le Chatelier's principle: A system under stress will react in a way to alleviate the stress and reestablish equilibrium.
The Law of Conservation of Mass: In a chemical reaction, the mass of the reactants always equal the mass of the products.

Phase 2: Analyze the efficiency of the novel method compared to a colorimeter and the Brick MUA Lab.

Methods
Phase 1: Key Reagent Discovery

Reactions Ran to Obtain Base Image:

I started with 24 chemical compounds for the novel method. The first box depicts 12 of the 24
compounds used. Based upon a compounds ability to form a nutrient precipitate I eliminated 2 of
the original 12 compounds (Box 2). Base upon a chemicals MSDS, I eliminated 6 of the 10
compounds that were harmful to the environment (Box 3). The deciding factor was a compounds
position on the activity series (Box 4). This process of elimination supported the hypothesis that
Sr(NO3)2, CaCl2, and Na2CO3 were potential key reagents for the novel method. Note since nitrates are
always soluble, the way to determine nitrate content based on precipitation was to precipitate
everything that are not nitrates and then use stoichiometry.

In order for a precipitate method to be used to detect nutrients, a base image that
indicates when the reaction is complete is needed. As long as the base image is
achieved for all future unknown samples, the reaction has gone to completion and
stoichiometry can be used to determine nutrient levels. To create the base images, I
reacted 1 Molar solutions of the key reagents with nutrients containing compounds
(indicated below). Note that nitrates are soluble so I precipitated strontium carbonate
and then calculated soluble nitrates.

Phase 1 : Key Reagent Discovery

Reactions Ran to Obtain Base Image

1. Possible Key
Reagents:

2. Forms a Nutrient
Precipitate:
Sr(NO3)2

Sr(NO3)2

Ca(NO3)2
MgSO4

MgSO4

CaCl2
Pb(NO3)2

Pb(NO3)2
BaCl2

BaCl2

AgNO3
Cu2SO4

Cu2SO
NaNO3

AgNO3

Sr(NO3)2
CaCl2

CaCl2
Na2CO3

Na2CO3

Ca(NO3)2

3. Environmental
Friendly:

Na2CO3

Sulfate Detection: Sr(NO3)2(aq)+ MgSO4(aq) -> Mg(NO3)2(aq) + SrSO4(s)

4. Highest

Phosphate Detection: CaCl2(aq) + Na2HPO4(aq) -> CaHPO4(s) + 2NaCl(aq)

Activity:

Nitrate Detection: Na2CO3(aq) + Sr(NO3)2(aq) -> 2NaNO3(aq) + SrCO3(s)

Sr(NO3)2
CaCl2
Na2CO3

CaCO3

K2CO3

Phase 2: Efficiency Analysis

Through numerous literature search, there has been no evidence of any relationship between the novel method created and current methods of nutrient
detection. Thus, I concluded that the novel method was a method that has never been used before- allowing me to name it the Zheng Precipitation Analysis or
Figure 4: Sulfate Base Image
Figure 5: Phosphate Base Image
Figure 6: Nitrate Base Image
PA Method for short.
To evaluate the capabilities of the PA Method (Phase 2), 48 water samples were gathered from the Metedeconk River, Brick NJ and from a Brick, NJ tap
water source once a week on Wednesday over six months from August 15, 2012 to January 23, 2013. This totaled 46 samples, not 48 samples as Hurricane
Sandy struck New Jersey on October 29-30, 2013, which was the day before a schedule sampling day. By gathering water from the Metedeconk River and from
the Brick MUA, I was able to utilize the Brick MUA State-Certified Lab to verify the readings from the Colorimeter and the PA Method. Thus, the Brick MUA Lab
was the control and the Colorimeter and the PA Method were the variables being compared to control.

Figure 15: Sample sulfate calculations

Applications and Future Research

Due to Hurricane Sandy, sample day #12, which was 1 week after Hurricane Sandy, was extremely turbid and had to be filtered with a vacuum pressure
pump attached to a filter flask attached to a funnel (Figure 8). To determine accuracy of the novel method compared to the colorimeter, detailed lab results
were obtained from Brick MUA Lab. In other words, the Brick MUA results are the control, while the novel method and the colorimeter are variables to be
tested for efficiency. Efficiency was evaluated on the basis of cost, accuracy, and speed (Phase 2). Overall efficiency is summarized and outlined in table 1.
Data regarding cost of the test were obtained from Brick MUA, LaMotte, and Carolina Supply Company.

Results

Conclusions

Figure 7: Satellite Image of Sample Site

Figure 8: Laboratory Setup of the Novel Method

Figure 9: LaMotte SMART 2 colorimeter

Figure 10: Vacuum pump used to remove sediments

The novel method involves a double displacement of Strontium nitrate, Calcium chloride,
and Sodium carbonate as key reagents. By adding the key reagents to any sample to
obtain the base coloration, the reactions have gone to completion (Clark 2002). By
measuring the amount of key reagent inputted and using mole ratios the amount of
nutrients present in a sample can be determined. Overall, the PA Method versus the
Colorimeter is 10 times faster, 23.48% more accurate, and 970 times cheaper. The PA
Method versus the Brick MUA Lab is 180 times faster, 3.83% error, 12,500 times cheaper.

Acknowledgements
Figure 11: Metedeconk River sulfate levels

Figure 12: Brick MUA tap water sulfate level

(ppm; + 5% Standard Error) from 8/15/12 to 1/23/13

(ppm; + 5% Standard Error) from 8/15/12 to 1/23/13

Figure 13: Metedeconk River phosphate levels

Figure 14: Brick MUA tap water phosphate level
(ppm; + 5% Standard Error) from 8/15/12 to 1/23/13
(ppm; + 5% Standard Error) from 8/15/12 to
1/23/13

Table 1: Chart depicting speed, accuracy, and cost among the colorimeter, Brick Lab, and the PA Method

Method

Phase 1: I hypothesize that by using Sr(NO3)2 to yield a sulfate

precipitate, CaCl2 to yield a phosphate precipitate, and Na2CO3,
to yield a counter nitrate precipitate along with stoichiometry, a
different approach can be create to measure nutrients.
Phase 2: I hypothesize that readings from the PA Method are
extremely accurate due to the Law of Conservation of Mass and
how reaction run to completion as long as the base image is
achieved.

= 15.36
ppm SO4

NaCl diffracts light from the colorimeter (LaMotte 2012). This may contribute to high
error for the Metedeconk River as it is a combinations of salt and fresh water. Although
the samples were obtained from a definite freshwater location, salt intrusion may have
occurred. This hints at the potential for the PA method to be used in saline water. As a
future study, the method can be tested on ocean water. A projected hypothesis to
colorimeter accuracy is ions dissociate in aqueous environments and the key reagents
binds to the nutrient ions and are not affected by NaCl. Furthermore, other future
research studies involving the PA method may include using the knowledge from this
study to create methods to detect other contaminants like bacteri. Furthermore, future
research studies could be conducted to elucidate the cause for 3.83% error in the PA
Method. In the 1990s, water treatment plants used an elementary form of precipitation to
detect nutrients. However, precipitation creates an unusable sample; thus, treatment
plants discarded precipitations and began to use colorimeter. Future research on
improving the PA Method to account for irreversible samples and decreasing the
percent error and increasing range of detection in the water may eventually place the PA
Method above the colorimeter. Utilizing the PA Method will promote faster and cheaper
nutrient monitoring around the world both on a industrial and residential scale.

-Crystalline Solids diffract

light
-Glass Cracks diffract
Phosphates (PO4-3)
light
-Expensive
-Requires 10 minutes to
Figure 3: Colorimeters emit a beam of light through a sample
runand determine nutrient contents
base upon absorbance; however, as colorimeter utilize optics
they are prone to error.
-Inaccurate

0.16 mL
Sr(NO3)2

CaCO3

Limitations
Sulfates (SO4-2)

The base images (Figures 4, 5, and 6) and water quality readings support the
hypothesis of Phase 1 and Phase 2 respectively. Discrepancies may be due to how the
colorimeter is subjected to many errors. Colorimeters use light rays to determine the
amount of nutrients in a sample. Light rays can be diffracted by finger smudges and
cracks in the glass vials. It may seem that the novel method may also be erroneous
because each drop of key reagent may vary in volume and people with shaky hands may
add excessive drops. However, surface tension of liquids will hold each droplet together
and insure that they have the same volume (Ho et al. 1996). Plus, error can also be
eliminated by using a standard micropipette.
Key reagents will bind to other ions but will not incur faulty readings because ions
dissociate in water (Ho et al. 1996). Continuous addition of the key reagent until the base
coloration is achieved insures that the nutrients are bound to the key reagent. The base
coloration will always be produced because equilibrium will always establish itself
(Clark 2002). The key reactants are specific for their nutrient because they must fit three
criteria. This ensures for a precipitate to allow for stoichiometry.
Hurricane Sandy struck the Jersey Shore on October 29-30, 2012 carrying wind gust
speeds of over 60 mph (Nutt 2013). Sample #12 was gathered on November 7, 2013, eight
days after Hurricane Sandy hit the Metedeconk River. The storm stirred up the river and
made it turbid. High turbidity cannot be ran. Thus, the sample had to be filter out to
remove sediments. Sediments contain pockets and holes that retain and attract the
negatively charged nutrient ions (Aprile and Lorandi 2012). Thus, when the sediments
were filtered out, so were the nutrients. This resulted in low readings eight days after
Hurricane Sandy when normally nutrient readings are expected to be high due to
excessive runoff from heavy rain.
Significance difference is the term used to describe a set of data that is
mathematically different. In all the test, the p-value for an ANOVA analysis was less than
0.05. This means that colorimeter readings were not a good representation of neither the
novel method nor the Brick lab. However, the novel method is a good representation of
the Brick lab. Graphically, this is depicted as error bars with 5% standard deviation.

CaCO3

Nitrates (NO3-1)
Light

Discussions

Figure 15: Metedeconk River phosphate levels

Figure 16: Brick MUA tap water phosphate level
8/15/12 to 1/23/13
(ppm; + 5% Standard Error) from 8/15/12 to 1/23/13

Speed (mins) Accuracy

Colorimeter

10

72.69%

Brick MUA Lab

180

Control

Novel Method

96.17%

Cost (per test)

$3.88 ($3.88 x
101)
$50.00 ($5.00 x
102)
$0.004 ($4.00 x
10-3)

(ppm; + 5% Standard Error) from

Acknowledgements go to the following people and organizations for their contributions to this study: Kelly
Kelsey and John Wnek of the Marine Academy of Technology and Environmental Science, Rob Karl of the
Brick Municipal Utility Authority, Monmouth Junior Science Symposium, and my family.

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