INTRODUCTION

This chapter provides a conceptual background and discusses selected studies which are

related to the study. It provides a basic understanding on the effects of chromium (VI) as a toxic

pollutant, the production of iron (II,III) oxide nanoparticles via green synthesis and the properties

of rice hull which makes it as reducing and capping agent.

Background of the Study

Clean water is one of the most important and basic natural resources. However, due to the

rapid rate of economic development in the Philippines, the discharge of domestic and industrial

wastewater, and the agricultural runoff has caused extensive pollution of the receiving water

bodies (Ahmad & Mahmoud, 2010).

Heavy metals contamination is a growing issue affecting living organisms throughout the

world. The rapid industrial development has caused a tremendous increase in the direct and

indirect discharges of heavy metals to the environment through wastewater (Khamis, 2009). In

industrial wastewater treatment, chromium, copper, cadmium, lead, zinc and nickel are

considered more toxic and are receiving more attention of researchers (Fu & Wang, 2011). The

toxicity and persistence in the environment of these elements have generated a significant threat

to public health.

Chromium is a harmful heavy metal and exists in various oxidative forms; however, the

trivalent and hexavalent states are considered more hazardous in terms of environmental

pollution point of view. Chromium (VI) is considered more harmful and toxic due to its high

carcinogenic and resistant properties than chromium (III) (Praveen & Loh, 2016) but still has a

significant presence in the environment. In fact, the water bodies surrounding mining operations
in Surigao, Philippines have a chromium (VI) presence of up to 140 mg/L (Panela, 2012). This is

about 3000 times greater than the World Health Organization (2003) provisional guideline for

total chromium in water.

To prevent this damage and to protect problems with the law, the wastewater should be

treated first before disposal. Different conventional methods are generally recommended for

chromium (VI) removal from the environment (Kobya, 2004). However, these processes are

costly and generate a variety of secondary pollutants. Many recent studies have indicated the

potential of metal oxide nanoparticles as effective agents for heavy metals removal in wastewater

treatment. Nanoparticles are materials with one, two or three external dimensions ranging from

approximately 1 nm to 100 nm (ISO, 2008). Among these metallic particles, the interest in using

magnetic particles such as iron (II,III) oxide for remediation of water and wastewater pollutants

is increasing due to its excellent properties (Herlekar et al., 2014).

In the synthesis of iron (II,III) oxide nanoparticles, chemical methods are conventionally

used which involve the usage of reactive and toxic reducing agents and formation of hazardous

byproducts (Saif et al., 2016). Not only these limited their environmental application but also

have highlighted the need to develop clean, non-toxic and environment friendly procedures for

iron oxide nanoparticle production. Synthesis via plants is a relatively straight forward and

advantageous approach because it is faster than any other synthesis protocols, more cost-

effective and is relatively easy to scale up for production of large quantities of nanoparticles

(Iravani, 2011). In addition, this approach is entirely eco-friendly and more feasible due to the

availability of local resources.

Plants which contain antioxidants can terminate chain reactions by removing free radical

intermediates, and inhibit oxidation reactions. Being oxidized by themselves, antioxidants are
often reducing agents such as thiols, ascorbic acid and polyphenols (Ashok, 2013). In this study,

rice hull, which is long considered a waste from the rice milling process and are often dumped

and/or burned here in the Philippines, is selected as the reducing and capping agent in the

synthesis of iron (II,III) oxide nanoparticles due to its high phenolic content (Butsat &

Siriamornpun, 2010). Rice hull extract also contains bioactive compounds and exhibits reducing

abilities (Liu, 2017).

Sand filters have been used for several years already to remove pathogens and suspended

solids from water (Elliott, 2008). The result of this study could be an innovation to the traditional

application of sand filters as point-of-use water treatment system. Through the addition of iron

(II,III) oxide nanoparticles, wastewater treatment could be improved through removal of toxic

heavy chemicals such as chromium (VI)

Statement of the Problem

The study was conducted to synthesize iron (II.III) oxide nanoparticles using rice hull as

reducing and capping agent; to utilize the synthesized iron (II,III) oxide nanoparticles as sand

composite filter for chromium (VI) removal; to confirm the identity of the synthesized iron

(II,III) oxide nanoparticles using VIS-Spectroscopy and Field Emission Scanning Electron

Microscope; to determine the percent removal of chromium (VI) in the two set-ups that is

prepared; and to evaluate whether there is a significant difference between the two set-ups.
 METHODOLOGY

Figure 2 shows the flow diagram of the experimental procedure that will be employed in

this study.

Preparation of the Synthesis of Iron Physical and Chemical

Rice Hull Extracts characterization of the
& Phenolic (II,III) Oxide Iron (II,III) Oxide
Content Test Nanoparticles Nanoparticles

Preparation of Sand Synthetic Pre-test Analysis

Composite with Iron
(II,III) Oxide Wastewater for the Chromium
Microparticles Preparation (VI) content

Filtration of % Removal
Synthetic Post-test and Calculation and
Wastewater in the Analysis Statistical Tool
Sand Filter Analysis

Figure 2. Schematic diagram of the experimental procedure

RESULTS AND DISCUSSION

This chapter presents the data, analysis and interpretation based on the results from the

determination of physical and chemical characteristics of iron (II,III) oxide nanoparticles

synthesized from the ferric chloride solution and rice hull extract as reducing and capping agent

and the experiment conducted on the removal of hexavalent chromium using the nanoparticles.

The experiment consisted of pre-test and post-test analysis having three trials each. The results

obtained were analyzed using statistical tool and presented in this chapter.

Phenolic Content Testing on Rice Hull Extract. Ferric chloride test was used to

determine whether phenolic compounds were present in the rice hull extract. This test states that
after addition of dilute ferric chloride, the formation of a red, blue, black, green, or purple

coloration indicates the presence of phenols.

Few drops of 1% aqueous ferric solution were added to 10 mL of prepared rice hull

extract and showed formation of intense green and black colors, which confirmed the presence of

phenolic compounds. Phenolic compounds in the rice hull extract act as reducing agent and

stabilizing agents in the synthesis of iron (II,III) oxide nanoparticles (Vilchis-Nestor et al., 2008).

Characterization of Synthesized Iron (II,III) Oxide Nanoparticles. Iron (II, III) oxide

nanoparticles were prepared in the presence of 8 mL of rice hull extract. Physical and chemical

characteristics of the sample in terms of its particle size, color and solubility at 25-30°C,

confirmed the presence of iron (II,III) oxide nanoparticles.

The range of the sizes of the produced nanoparticles was determined by the use of Field

Emission Scanning Electron Microscopy (FESEM) and further analyzed using the Image J

software.

Figure 5 showed the result of the FESEM analysis of the iron (II,III) nanoparticles

synthesized using 8 mL of rice hull as reducing and capping agent, where it can be observed that

the nanoparticles were quasispherical in shape, have rough surfaces and are varying in sizes.
Figure 5. FESEM image of the synthesized iron (II,III) oxide nanoparticles.

The diameter of the synthesized nanoparticles was determined using r=

√ A
π
and then

multiplying r by 2 (Dune Sciences, Inc., 2011). Table 1 shows the area and particle diameter of

the synthesized iron (II,III) oxide nanoparticles, with the largest being 96.5001 nm and the

smallest, 17.905 nm. On average, the particle diameter for the synthesized magnetite

nanoparticle is 44.2860 nm that used 8 mL of rice hull extract, which falls within the established

range of nanoparticles being 1-100 nm (ISO, 2008). Variations in mean particle diameters with

other studies may be caused by the differences in process chosen, purpose of the product, and the

kind and amount of reagents added. Rice hull extract was used to prepare iron (II, III) oxide

nanoparticles to reduce the average nanoparticle size (Vilchis-Nestor et al., 2008).

Table 1.

Particle Size of iron (II,III) oxide nanoparticles using Field Emission Scanning Electron

Microscopy (FESEM), analyzed using ImageJ application.

Particle
Particle No. Area (sq. nm)
Diameter (nm)
1 251.72 17.9025
2 257.713 18.1143
3 319.644 20.1738
4 387.569 22.2141
5 485.46 24.8617
6 559.378 26.6875
7 559.378 26.6875
8 561.375 26.7351
9 573.362 27.0190
10 623.307 28.1712
11 745.171 30.8023
12 817.091 32.2545
13 1536.291 44.2274
14 2772.915 59.4187
15 3480.128 66.5660
16 3819.751 69.7384
17 4257.264 73.6241
18 5783.566 85.8129
19 6111.201 88.2100
20 7313.863 96.5001
Average 2060.80735 44.2860

The jet black color of the iron (II,III) oxide nanoparticle was confirmed using optical

microscope at University of San Carlos which is shown in Figure 6.

 Figure 6.

Optical

microscope

image of the

synthesized

nanoparticle.

The solubility of the iron (II,III) oxide nanoparticles was tested by adding 5 mL of water

to a test tube containing 3 mg of the magnetite particles and was shaken vigorously. No

dissolution of the nanoparticles was observed. The obtained sample also showed attraction to a

strong magnet, which is also another confirmation that it is magnetite in form. The results

showed similarities with that of Lee (2007), Entrata et al. (2017) and Tang & Lo (2013).

Therefore, the use of rice hull as reducing and capping agent for the synthesis of iron (II,III)

nanoparticles was successfully showed.

Removal of Hexavalent Chromium in the Synthetic Wastewater. The removal of

hexavalent chromium was done by allowing the prepared synthetic wastewater to pass through

the sand filter and sand composite with iron (II, III) oxide nanoparticles. The concentration after

the passage was measured using Visible (Vis) Spectroscopy using 1,5-diphenylcarbazide method.

The experiment was evaluated using three trials for each set-up. Table 2 shows the

performance of the filter using sand only (Set-up A) on the removal of chromium (VI) in terms
of concentration (mg/L). Both pre-test and post-test results were recorded. The percent removal

was calculated by subtracting the final chromium (VI) concentration from the initial

concentration and dividing the difference by the initial concentration. The average concentration

for the post-test analysis of the said set-up showed little difference on the chromium (VI)

content, with only a decrease of 0.146 mg/L from the initial concentration, which resulted to a

percent removal of 5.19%. According to Fadali et al. (2004) and Gupta and Babu (2006) on the

percentage removal of chromium (VI) using sand as adsorbent, it was found that the chromium

(VI) removal decreases as the amount of sand is increased. This demonstrates the incompatibility

of sand as an adsorbent for highly concentrated hexavalent chromium solutions.

Table 2.

Control Group Results (Set-up A) on the Hexavalent Chromium Concentration of Synthetic

Wastewater Sample

Trial Pre-test Values (mg/L) Post-test Values (mg/L)

1 0.152 0.147
2 0.154 0.149
3 0.156 0.142
Mean 0.154 0.146
SD 0.002 0.0036

Studies have shown that iron (II,III) oxide nanoparticles are efficient adsorbents because

they combine magnetic separation with ionic exchange capacity for heavy metals removal

(Velez, 2016). The results from the trials of Set-up B which used sand composite with iron

(II,III) oxide nanoparticles have shown an increase in relation to the removal of hexavalent

chromium, as presented in Table 3. Pre-test and post-test values were also compared and

recorded. In all the trials for this set-up, the content of chromium (VI) has decreased greatly after
the synthetic wastewater was passed through the sand composite filter. The percent removal of

Set-up B was computed using the same procedure as that of the first set-up, indicating a

favorable chromium (VI) removal of 46.10%. The high removals obtained, in case of iron (II,III)

oxide and sand system, can be mainly attributed to the chemical reduction of chromium (VI) to

chromium (III) and adsorption of chromium (VI) by iron metal. In addition to its high reaction

affinity to chromium (VI), iron expectedly provides very large reactive surface area, thus,

enhancing further eradication of hexavalent chromium from solution. The reduction reaction of

dichromate by iron is a heterogeneous reaction and pH dependent. It can also be quantitative and

extremely fast (Chang, 2004).

Table 3.

Sand Composite Results (Set-up B) on the Hexavalent Chromium Concentration of Synthetic

Wastewater Sample.

Trial Pre-test Values (mg/L) Post-test Values (mg/L)

1 0.152 0.083
2 0.154 0.087
3 0.156 0.079
Mean 0.154 0.083
SD 0.002 0.004

Statistical analysis was used to compare the differences in post-test average

concentrations of chromium (VI) between Set-up A and Set-up B. T-test for two independent

means was utilized to determine a significant difference in the performance between the two

groups in terms of chromium (VI) removal as shown in Table 3. The control group using sand

only was associated with an average final chromium (VI) concentration of 0.146 mg/L. By

comparison, the sand composite with iron (II,III) oxide nanoparticles was associated with a

numerically smaller average final chromium (VI) concentration of 0.083 mg/L. Based on the t-
test conducted at an alpha of 0.05, t-Stat value which was 20.2629 is greater than the computed

critical value which was 2.7764. This result indicated that the alternative hypothesis must be

accepted, which suggest that the sand composite with iron (II,III) oxide nanoparticles has

significantly reduced the chromium (VI) content as compared to using sand only.