UEMX 3613 ENVIRONMENTAL SCIENCE AND ENGINEERING

Lecturer : Dr. Ong Ying Hui

Experiment Number : 3
Date of Experiment : 25/3/2016

No Name Student ID
1. Ng Jia Ying 1205213
2. Menaga A/P Jayabalan 1305534
3. Lee Chee Yin 1500864
4. Lim Sin Wai 1204377
5. Lim Ming Shern 1407505
Received by :

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Receipt of Lab Report Submission (to be kept by
student)
Experiment Number : 3
Date of Experiment : 25/3/2016
No Name Student ID
1. Ng Jia Ying 1205213
2. Menaga A/P Jayabalan 1305534
3. Lee Chee Yin 1500864
4. Lim Sin Wai 1204377
5. Lim Ming Shern 1407505

Received by :
EXPERIMENT 3: DETERMINATION OF CHLORIDE, SULPHATE, AND
NITRATE IONS
OBJECTIVES OF EXPERIMENT

To analyze the concentration of chloride, sulphate, and nitrate ions in tap water and fish
tank water samples by using HACH DR 2800 Spectrophotometer

INTRODUCTION

Acid rain is a mixture of deposited materials from the atmosphere which contain higher
amount of nitric acid and sulfuric acid. Formation of acid rain is mainly due to fossil fuel
combustion which results in primary emissions of sulfur dioxide and nitrogen dioxide.
Acid rain causes major negative impact for the overall biological system on Earth. PH
value of rainwater indicates how acidity it is and the effects of acid rain on aquatic lives,
buildings can be investigated. Natural acidity of precipitation represents the PH value of
pure water in equilibrium with atmospheric concentration of carbon dioxide. The transport
of acidic substances and their depositions are controlled by atmospheric processes.

This experiment involves the determination of chloride, sulfate and nitrate ions in
environmental water samples such as tap water and aquarium water in order to evaluate the
overall quality of these water samples. Anion concentrations in water samples or natural
water vary accordingly to hydrological and seasonal conditions. HACH DR 2800
spectrophotometer is a device used to measure the concentrations of anions present in these
water samples as milligrams per liter (mg/L).

Nitrates in water samples cannot be detected without testing as it is colourless, odorless

and tasteless. Nitrate is known as nitrate-nitrogen which means the amount of nitrogen in
the form of nitrates. Nitrate-nitrogen occurs naturally in groundwater with a low
concentration.

Sulfate is a combination of sulfur and oxygen. It is known as naturally occurring minerals

in some soil that contains groundwater. Sulfate also causes buildup in water pipes and rises
bitter taste in water. Sulfur-reducing bacteria chemically change natural sulfates to
hydrogen sulfide.
Chloride ions is one of the major inorganic anions in water and wastewater. The chloride
concentration is higher in wastewater than in raw water. The measured chloride ions can be
used to know salinity of different water sources. Chloride ions maybe present in higher
concentration along the seaside due to leakage of salt water into the sewage system.

MATERIALS AND EQUIPMENT

HACH DR 2800 Spectrophotometer

Sample Cells
Deionized Water
Tap Water
Fish Tank Water
SulfaVer 4 Reagent Powder Pillows, 10-mL
Mercuric Thiocyanate Solution
Ferric Ion Solution
NitraVer 5 Nitrate Reagent Powder Pillow.,10-mL
Micropipette

RESULTS AND CALCULATIONS

Table 1 : Results for Mercury Thiosulphate Method

Sample Dilution Concentration of Chloride Ions (mg/L Cl-)
Factor,P Reading 1 Reading 2 Average
Tap Water 1 4.8 3.6 4.2

Diluted Fish 5 7.1 5.2 6.15

Water
Table 2 : Results for SulfaVer 4 Method

Sample Dilution Concentration of Sulphate Ions (mg/L SO42-)

Factor,P Reading 1 Reading 2 Average
Tap Water 1 16 15 15.5

Fish Tank Water 1 23 22 22.5

Table 3 : Results for Cadmium Reduction Method

Sample Dilution Concentration of Nitrate Ions(mg/L NO3-)

Factor,P Reading 1 Reading 2 Average
Tap Water 1 -1.2 -0.3 -0.75

Fish Tank Water 1 7.3 7.6 7.45

Concentration ( mgL )=Concentration of Diluted Sample ( mgL ) Dilution Factor

Concentration ( mgL )=7.1( mgL ) 5

mg
35.5
L

Table 4 : Revised Results for Mercury Thiosulphate Method

Sample Dilution Concentration of Chloride Ions (mg/L Cl-)
Factor,P Reading 1 Reading 2 Average
Tap Water 1 4.8 3.6 4.2
 Fish Tank 1 35.5 26.0 30.75
Water

Table 5 : Revised Results for Cadmium Reduction Method

Sample Dilution Concentration of Nitrate Ions(mg/L NO3-)

Factor,P Reading 1 Reading 2 Average
Tap Water 1 <0.1 <0.1 -

Fish Tank Water 1 7.3 7.6 7.45

DISCUSSION

As observed from the experimental results, concentration of chloride, sulphate and

nitrate ions are higher in fish tank water compared to the conventional tap water. From
Table 1, the chloride ions in fish tank water is higher even after a dilution of 5 times. The
reason for the dilution, is because the sensitivity, or detection range of DR 2800, HACH
Spectrophotometer is merely from 0.1 mg/L Cl- to 25.0 mg/L Cl-, which is out of the range
of the undiluted fish tank water. Dilution factor of 5, means a 1:5 dilution, 1 part of fish
tank water, + 4 parts of diluent, in our case deionized water. To obtain the concentration of
chloride ions in fish tank water, the concentration of chloride ions in diluted fish tank water
is multiplied with the dilution factor. As observed in Table 3, the concentration of nitrate
ions in tap water is of negative value. This is because, the real concentration of nitrate ions
in tap water is simply too low, and is out of detection range of the spectrophotometer
which ranges from 0.1 mg/L NO3- 10.0 mg/L NO3- . The concentration of nitrate ions in tap
water is actually less than 0.1 mg/L NO3-. Higher values of all three ions in fish tank water
is due to the prolonged exposure of fish tank water to the environment, which may be
caused by many factors while the tap water had just been processed and filtered and thus
the low concentration of ions.

Aquarium nitrate can be identified easily, by observing the green aquarium water,
due to algae outbreaks. Algae feeds on nitrate and the greener the aquarium seems, the
higher the concentration of nitrate. Nitrate is a main ingredient for plant fertilizers, thus
should always be used with care. Fish food is another unavoidable nitrate sources in the
aquarium, and know that the higher the protein level of fish food, the higher the
concentration of nitrate as well. If a fish food goes uneaten, it eventually decays, resulting
in an increase in nitrate levels.

The high chloride ions concentration is fish tank water is due to usage of salt. It is
claimed by many that, salt, sodium chloride is used as preventative measure against
parasitic infestations. Salt also gives other benefits such as healing wounds of fish, reduces
ostomic pressure and so on. Another contributor of chloride to the fish tank water, is the
tap water, which is usually used to replace the fish tank water. Chloride is dosed into tap
water during the filtration or cleaning process, as chloride disinfects and deactivates most
microorganisms. The sulfate ions in tap water and fish tank water are both relatively high,
most probably due to runoff of fertilizer from agricultural uses into groundwater, and are
not removed properly. Decorations in aquariums, such as rocks and decorative corals,
causes sulfate ion concentration to increase as well.

Chloride, sulfate and nitrate are the ions found inside the water contents. The
concentration of these ions in the water is contributed by several sources. First of all,
chloride ions contents are mainly due to the presence of salt inside the water. It is
originates from the dissociation of salts such as sodium chloride or calcium chloride in
water. Chloride ions can be found from both natural and anthropogenic sources such as
run-off containing road deicing salts, inorganic fertilizers, landfill leachates, animal feeds
and seawater intrusion in coastal areas. In addition, foods such as fish feeds contained
chloride ions concentration at a level normally less than 0.36 mg/g. Furthermore, addition
of salt while processing, cooking or eating will increase the chloride level in food. Besides,
the road salt which contained mostly of sodium chloride is readily dissolves and will enter
aquatic environments in ionic forms. Therefore, the concentration of chlorine ions will be
higher in fish water than in the tap water.

Other than that, sulfate ions also made up a portion of total ions inside the water
contents. Sulfate ions are the combination of sulfur and oxygen. It is found naturally in
some soils and rocks. It occurs in numerous minerals such as barite and gypsum.
Therefore, when groundwater moves through these matters, some sulfates will dissolve
into the water. Moreover, run-off from fertilized agricultural lands also contributes sulphate
ions to water bodies. Besides that, sulphate can also be discharged into water from mines,
smelters, paper mills and textile mills. Combustion of fossil fuels generates sulphur dioxide
in the atmosphere and this may then contribute sulphate content to the water surface. In
water treatment process, aluminium sulphate which used as a sedimentation agent also will
discharge sulphate ions into the water content. Furthermore, sulphate can also be
contributed by copper sulphate which used to control the algae growth in raw water
supplies.

Nitrate is an oxide of nitrogen and it is the primary source of nitrogen for plants
which occurs naturally in soil and water. One of the main sources of nitrate contributor to
the water bodies is from nitrogen fertilizers which are normally used for soil enrichment.
This is caused by run-off of nitrogen fertilizer when nitrates ions from fertilizers are
carried by rain water or irrigation through the soil into the groundwater. Besides, nitrates
can also be discharged into the water through municipal and industrial waste water, refuse
dumps, animal feedlots, septic tanks and decaying plant debris. Moreover, concentration of
nitrate also can influence by geologic formations and direction of ground water flow.
Therefore, when these contaminated groundwater flow into streams and rivers, an
increased in nitrate concentration will happen in the water bodies downstream. (Priscilla,
W., 2015)

The industrial and agricultural wastewaters that are generated may contain large
amount of chlorides ion. Excessive intake of water including chloride ions poses human
health risk and disruption in ecological balance of the affected area. Therefore, many
techniques have been adopted in order to reduce the concentration of chlorides in waste
water like demineralization, reverse osmosis, electrodialysis and so on. Reverse osmosis
(RO) is a process of demineralize or deionize water by pushing it under pressure through a
semi-permeable membrane. It can be done by forcing a solvent from a region of high
solute concentration through a membrane to a region of low solute concentration. Reverse
osmosis will remove 90 - 95% of chlorides because of its salt rejection capabilities.

Besides, Electrochemical Chloride Extraction (ECE) is a simple electrochemical

process which implies the basic principle of ion migration towards oppositely charged
poles. The apparatus contained an anode which was inserted in an electrolyte media on a
concrete surface. The anode and the reinforcing steel were made positively charged by
connecting to direct current(DC). The chloride ions will attracted to the anode field
occurred, thereby reducing the chloride content in the concrete. At the termination of the
process, chloride free, highly alkaline concrete is obtained, which results in strong
repassivation of the embedded reinforced steel and halting of the corrosion of the same. A
study was conducted in order to observe the free chloride content in a concrete block
during electrochemical chloride removal. It showed that, due to the free chloride removal,
bound chloride is dissolved in order to reestablish the equilibrium between bound and free
chloride (Elsener B., Angst U., 2007)

Many industrial wastewater especially those associated with mining and mineral
process will contain high concentration of sulfate. There are several ways to remove sulfate
ions such as reverse osmosis, distillation and ion exchange system and so on.

As the reverse osmosis (RO) process discussed previously, it is a water treatment

system which forcing the water flow through a cellophane-like plastic sheet. Besides,
distillation is a treatment system that boils water then cools the steam until it condenses
into a separate container. The dissolved sulfate are left behind in the boiling pot.
Distillation units can remove almost 100% of sulfate. Ion exchange (IE) is the most
common method of removing large quantities of sulfate from water for commercial,
livestock, and public supplies, but is not commonly used for individual household water
treatment. It is a process where one element or chemical is switched for another. Sulfate
ions in the water exchange places with other ions, usually chloride, which is on the resin.
When the resin is full to capacity with sulfate, it must be "regenerated" with a salt solution.

Nitrate ions are highly soluble and hence it is not amenable to removal by
coagulation and precipitation or adsorption and filtration. There are some water treatment
processes to overcome the high concentration of nitrate ions that are ion-exchange and
heterotrophic biological denitrification.
 In ion-exchange denitrification water is passed through a bed of synthetic resin
beds which remove nitrate from the water, exchanging them for equivalent amounts of
chloride. Once the exchange capacity of the resin is reached, the resin bed is taken out the
regenerated using sodium chloride solution (brine). After rinsing with clean water the bed
is ready to use again. The spent regenerant contains a high concentration of sodium
chloride together with the anions (nitrate and sulphate) removed from the resin bed.

Biological denitrification shows the ability of certain naturally-occurring bacteria to

use nitrate for respiration under anoxic conditions (absence of oxygen). (Fanning J.C. ,
2000) The overall process is the reduction of nitrate to nitrogen gas and proceeds as
follows:

NO3- NO2- NO N2O N2

Denitrification can be worked using both heterotrophic and autotrophic bacteria. In

heterotrophic denitrification an organic carbon substrate, such as methanol, ethanol or
acetic acid, is required as a food source for the bacteria. In autotrophic denitrification an
inorganic energy source such as sulphur, reduced sulphur species (e.g. thiosulphate) or
hydrogen is required whereas the carbon needed for bacterial growth is obtained from
bicarbonate in the water.

CONCLUSION

Two water samples, fish tank water and tap water are analyzed for the concentration of
three ions, which is nitrate, chloride and sulphate ions. Results show that these ions are
more dominant in the fish tank water, as fish water are exposed to the environment which
contributes to these ions, for example fish foods, aquarium rocks, fertilizers for aquarium
plants, or even excretion from the fish.

REFERENCE
1. Elsener, B. and Angst, U. (2007): Mechanism of electrochemical chloride removal,
Corrosion Science, 49(12):4504 4522.
2. Fanning, J.C. 2000 The chemical reduction of nitrate in aqueous solution.
Coordination Chemistry Reviews, 199, 159-179.
3. Priscilla, W. (2015, August 26). Nitrate in Drinking Water. Retrieved March 30,
2016, from
http://www.deq.state.or.us/wq/pubs/factsheets/groundwater/nitratedw.pdf
4. Sodium and Chloride in Drinking Water. (2010). Retrieved March 30, 2016, from
http://des.nh.gov/organization/commissioner/pip/factsheets/dwgb/documents/dwgb-
3-17.pdf
5. Sulfate in Drinking-water. (2004). Retrieved March 30, 2016, from
http://www.who.int/water_sanitation_health/dwq/chemicals/sulfate.pdf
6. Water Quality: Salinity and Chloride. (2006, May 26). Retrieved March 30, 2016,
from http://www.ruf.rice.edu/~cbensa/Salinity/