Kenneth John Anthony D.

Tabag April 22, 2019

Title: Performance Evaluation of Corn cob-derived Activated Carbon on the Removal of Mercury and
Lead on Contaminated Water

Review of Related Literature

Water Scarcity

Based on Human Development Report 2006, around 1.2 billion people, or almost one-fifth of the world
population, live in the area of scarcity. And another 1.6 billion people or almost one-quarter of the
world’s population face economic water shortage. Nearly half the global populations are already living in
potential water scarce area at least one month per year and this could increase at some 4.8 - 5.7 billion
on 2050. And about 73% of the affected people live in Asia (Burek et al., 2016) appeared on the news
reported by National Center for Groundwater Research and Training, 2018.

Around 700 million people in 43 countries suffer today from water scarcity (Human Development Report
2006). And third of the world’s biggest ground water system are already in distress according to (Richey
et al., 2015).

Philippine is an archipelago that comprises over 7,600 islands with a total land area of 300,000 square
kilometers as stated by (Gultiano, S. et al., 2003 ). As of 2014, the country has 4,785 renewable internal
freshwater per capita, it is 72% lower than as of 52 years ago based on the Food and Agriculture
Organization, AQUASTRAT data.

On the report submitted by ABS-CBN News on July, 2017, the Philippines has 91% of 100.7 million
people has an access to at least basic water service. But in Metro Manila, it is not advisable to drink tap
water for some reasons that it may be contaminated although they used it for cleaning and brushing
teeth, it is advisable to drink bottled water which is very expensive (Philippine Premier, 2016) and 21 %
of Filipinos fall below the poverty line that is 21 million people as of 2015 (Asian Development Bank,
2015). Therefore the availability and access to clean water varies within economic status.

Heavy Metals

The criteria used to define a heavy metal include density, atomic weight and atomic number as the
toxicity of a metal is connected to its atomic weight (Duffus, 2002). Heavy metals are chemical elements
with a specific gravity that is at least 5 times the specific gravity of water and have atomic weight
greater than that of sodium (Hawkes, 1997). Among the major heavy metals in waste water include
cadmium, lead, arsenic, iron and mercury, their toxicity can result in damaged or reduced mental and
central nervous function, lower energy levels, and damage to blood composition, lungs, kidneys, liver,
and other vital organs (Br. Med Bull, 2003). Long-term exposure may result in slowly progressing
Kenneth John Anthony D. Tabag April 22, 2019

physical, muscular, and neurological degenerative processes that mimic Alzheimer's disease, Parkinson's
disease, muscular dystrophy, and multiple sclerosis. Allergies are not uncommon and repeated long-
term contact with some metals or their compounds may even cause cancer (Michael McCally, 2002).

Sources of Lead and Mercury Contamination

Hg and Pb are naturally occurring elements in the earth’s crust and are common water contaminants;
they are released into the environment through the excessive use of several industrial, agricultural,
domestic and technological application. Prominent sources are mining, foundries and smelters and
other metal-based industry. Since they naturally occurring earth crust’s they also deposits in the sources
of water such as ground waters and spring through metal corrosion, atmospheric deposition and soil
erosion, volcanic eruption and weathering are also reported sources based on (Tchounwou, P. et al,.
2012).

Lead and Mercury Pollution in Davao Region

Small-scale gold mining activities utilizing mercury is being actively undertaken in provinces namely;
Benguet, Camarines Norte, Negros Occidental, Zamboanga del Sur, Zamboanga del Norte, Agusan del
Sur, Agusan del Norte, Surigao del Norte, Davao region and Palawan (Narvaez D, 2002). And among
Davao region, Municipality of Maco, Nabunturan, Pantukan, Monkayo, Manay and Lupon has been
identified for having intensive usage of mercury (Orbeta A.C, et al,. 2000).In Tagum City, gold refinery
and processing plant where also reported in operation, in fact during the Health assessment for mercury
exposure among schoolchildren residing near a gold processing and refining plant in Apokon, Tagum,
Davao del Norte, Philippines conducted by (Hirokatsu A, et al,. 2000), they have found out that levels of
total mercury for all water samples and sediments exceeded the national and international limits.
Results obtained for total mercury ranged from 0.55 to 1.36 μg /g dry wt., and the standard limit for
usable water is 0.001 mg/L (PSDW, 2014) and acceptable for residential land 1.0 mg/kg dry wt. (Morgan,
H. et al., 2009) which clearly showed that sample exceeds the limiting values and conclude that the area
is contaminated.

Hesperian Health Guide, 2016 reported that chemicals and minerals used in mining include cyanide,
sulfuric acid and heavy metals such as mercury, uranium, and lead, fuel such as gasoline, and diesel
which has also contain lead-mixture additive. These chemicals are then found in tailing, these the
byproduct left over from mining and extracting ores, dumping these tailing into no proper places could
brought these chemicals into animal and human contact, (CBC News, 2014). As reported, Philippines is
one of the largest mineral-rich countries, it ranks fifth on copper-gold deposits in the world, (Manila
Times, 2017). Davao region has many smale-scale mines who uses and dispose these chemicals (Drasch,
G. etal,. 2000), it is now safe to assume that water sources near mining site may have been
contaminated in alarming quantity.

Lead and its Effects

Lead is one of the toxic heavy metals in our environment. It occurs naturally in the earth crust inform of
lead sulphide (galena), lead anglesite (lead sulfite) or cerussite (lead carbonate). Inorganic form of lead is
Kenneth John Anthony D. Tabag April 22, 2019

found in old paints, soil, dust and various consumer products. Organic form of lead occurs in leaded
gasoline in form of tetra – ethyl lead (Landrigan, 2007)

Based on the report submitted by World Health Organization on August, 2018, Lead exposure can have
serious consequences for the health of children. At high levels of exposure, lead attacks the brain and
central nervous system to cause coma, convulsions and even death. Children who survive severe lead
poisoning may be left with mental retardation and behavioural disorders. At lower levels of exposure
that cause no obvious symptoms, and that previously were considered safe, lead is now known to
produce a spectrum of injury across multiple body systems. In particular lead can affect children’s brain
development resulting in reduced intelligence quotient (IQ), behavioural changes such as reduced
attention span and increased antisocial behaviour, and reduced educational attainment. Lead exposure
also causes anaemia, hypertension, renal impairment, immunotoxicity and toxicity to the reproductive
organs. The neurological and behavioural effects of lead are believed to be irreversible.

Mercury and its Effects

Mercury exists in various forms: elemental (or metallic) and inorganic (to which people may be exposed
through their occupation); and organic (e.g., methylmercury, to which people may be exposed through
their diet). These forms of mercury differ in their degree of toxicity and in their effects on the nervous,
digestive and immune systems, and on lungs, kidneys, skin and eyes.

Based on World Health Organization from their article entitled “Mercury and Health”, Neurological and
behavioral disorders may be observed after inhalation, ingestion or dermal exposure of different
mercury compounds. Symptoms include tremors, insomnia, memory loss, neuromuscular effects,
headaches and cognitive and motor dysfunction. Mild, subclinical signs of central nervous system
toxicity can be seen in workers exposed to an elemental mercury level in the air of 20 μg/m^3 or more
for several years. Kidney effects have been reported, ranging from increased protein in the urine to
kidney failure.

Water Treatment Methods

Ion exchange

Ion exchange is a water treatment method where one or more undesirable contaminants are removed
from water by exchange with another substance. Both the contaminant and the exchanged substance
must be dissolved and have the same type of electrical charge (Alguacil, 2003). When contaminants
dissolve in water they form ions. Ions are electrically charged portions of a compound. There is a
balance of positively and negatively charged ions in natural waters (Mollah et al., 2001).

This process brings together remarkable advantages: selectivity, sustainability, economy, safety,
simplicity and applicability on the removal of lead (Lalmi, A. et al., 2018). The disadvantage of this
method is that it cannot handle concentrated metal solution as the matrix gets easily fouled by organics
Kenneth John Anthony D. Tabag April 22, 2019

and other solids in the wastewater. Moreover ion exchange is nonselective and is highly sensitive to the
pH of the solution (Babel et al., 2006).

Electrodialysis

Electrodialysis is an electrochemical process in which ions migrate through ion selective semi permeable
membranes as a result of their attraction to two electrically charged electrodes able to remove most
charged dissolved ions (Strathmann, 2001). The process uses direct current power to remove salts and
other ionized species through cation and anion ion selective membranes. Electrodialysis is very useful
for water treatment: removal of mineral salts, sulfate and nitrate from water and sea water (Amado et
al., 2008). The electrodialysis is also a simple process to remove nitrate from ground water
(Elmidaoui et al., 2001)

Floatation

Flotation is a process that involves producing small air bubbles in the water being treated (Emamjomeh
and Sivakumar, 2009). The bubbles then attach to particles produced by coagulation and flocculation.
The resulting particles float to the surface of the water where they accumulate as a floating layer of
sludge, known as float, before being removed. Flotation in wastewater and domestic sewage treatment
offers process advantages over filtration, precipitation, adsorption onto natural and 15 synthetic
adsorbents. Advantages include better treated water quality, rapid start up, high rate operation, and a
thicker sludge (Babel et al., 2003).

Adsorbent

An adsorbent is a substance usually porous in nature with a high surface area that can adsorb
substances onto its surface by intermolecular forces (Chaudhari et al., 2003). Adsorbent materials have
an affinity to certain ions or ion groups and have shown high selectivity, resistance to degradation, high
temperatures and high levels of radiation (Abdel et al., 2007). During adsorption, solutes distribute
themselves between the adsorbent surface and the dispersing medium. Due to the presence of
functional groups, sorbents can be derivertised to improve their efficiency and increase their adsorption
capacity (Hong et al., 2002)

Sorption Studies

Adsorption is a separation process in which certain components of the fluid phase are transferred to the
surface of the solid adsorbents (Satya et al., 2012). When a solid surface is exposed to a fluid phase, the
molecules from the bulk of the fluid phase have tendency to accumulate or concentrate at the surface of
a solid (Satya et al., 2012). The phenomenon of the enrichment of chemical substances at the surface of
a solid is called ‘adsorption’. All adsorption performance processes are depends on solid-liquid equilibria
and on mass transfer rates (Hui et al., 2009). If the mass transfer is in opposite direction then it is called
as ‘Desorption’. Most adsorbents are highly porous materials, and adsorption takes place primarily on
the walls of the pores or at the specific sites inside the particle (Cederberg et al., 1985). Separation
occurs because differences in molecular weight, shape, or polarity cause some molecules to be held
Kenneth John Anthony D. Tabag April 22, 2019

more strongly on the surface than others or because the pores are too small to admit the larger
molecules (Cederberg et al., 1985).

Factors Affecting Adsorption

Adsorption of heavy metals from aqueous solutions depends on several factors. Factors which were
investigated in this study were; shaking speed, initial metal ion concentration, adsorbent dose and
temperature. These factors are briefly discussed in the following subsections

Effect of shaking speed

Adsorption of metal ion is affected by the shaking (agitation) speed, the higher the shaking speed the
higher the rate of adsorption. This can be explained by the fact that as the agitation speed is increased,
it increases the resistance of mass transfer between the solution and the adsorbent. The percentage
removal efficiency of metal ions also increases with increase in shaking speed though at different rate
for different metal ions which can be explained by different molecular sizes of metal ions (Singh et al.,
1985).

Effect of adsorbent dose

Adsorption of metal ions from aqueous solution is also affected by the adsorbent dose in that as the
adsorbent dose is increased the rate of adsorption also increases. Increasing the adsorption dosage
increases the surface area which makes it possible for more metal ions to be adsorbed.

Effect of temperature

Temperature is also another factor which affects the adsorption of metal ions. The percentage removal
efficiency decreases with increase in temperature. At low temperatures the adsorption capacity is very
high which may imply that adsorption of metal ions is a exothermic reaction (Viraraghavan and Kapoor,
1995). In any chemical reaction, increasing the temperature enables equilibrium to be attained within a
short time.

Effect of contact time

The effect of contact time on the removal of metals to reach equilibrium varies depending on the type
of metals. As the time increases, more amounts of metal gets adsorbs onto the surface of the adsorbent
and surface area available decreases.

Corn cobs

Maize or corn is a common name for cereal grass grown for food or livestock folder (Muthusamy et al.,
2012). Maize is one of the world’s chief grains. In Philippines it is grown almost in all parts of the country
as a matter of fact it is the second largest crop produced next to rice (Gerpacio, R.V. et al., 2004). After
the maize grain has been harvested, the maize stalks are used to feed animals, maize cobs which are
produced in large numbers in the country find very minimal use in our homesteads, low percentage of
Kenneth John Anthony D. Tabag April 22, 2019

the maize cobs are used as fuels the rest are found in large piles in our homesteads. Accumulation of
these maize cobs leads to environmental pollution.

Cobs can be used in factories for cleaning dampers and ventilation grates (Tin Win, 2005). Corn cob grit
is a safe blasting media for delicate parts. Corn cob grit abrasive will remove surface contamination,
debris, and coatings with little to no impact on the substrate. It is resistant to break down and can be re-
used multiple times in the blasting process. It is a biodegradable, organic blasting media that is obtained
from the hard woody ring of the cob. It is available in a variety of grit sizes and presents no health or
environmental hazards, additional feature is that they are naturally sourced and a good adsorbent
(Kramer Industry, 2018).

Cobs are composed of cellulose, lignin, semi-cellulose, extractives and ash and are made up of the
bonding between carbon, nitrogen, oxygen, sulfur, and hydrogen (Fang Zhen, 1993). They are porous in
nature which makes it a good choice for adsorption processes. Additional carbonization through
pyrolysis plus physical and chemical activation of cobs will greatly increase its porosity and surface area
reaching few square meters per gram (Sevilla et al,. 2011) and makes this material a subject for
researcher’s utilization.
Kenneth John Anthony D. Tabag April 22, 2019

References:

1. Br. Med Bull. (2003). Hazard of Heavy Metal Contamination. Pubmed. Retrieved from
http://www.ncbi.nlm.nil.gov/m/pubmed/14757716/
2. Human Development Report 2006. UNDP, 2006. Coping with water scarcity. Challenge of the
twenty-first century. UN-Water, FAO, 2007
3. National Center for Groundwater Research and Training. ( 2018). World Water Day. News and
Media. Retrieved from http://www.groundwater.com.au/news_items/world-water-day-march-
22-2018
4. Richey, A. S., B. F. Thomas, M.-H. Lo, J. T. Reager, J. S. Famiglietti, K. Voss, S. Swenson, & M.
Rodell (2015). Quantifying renewable groundwater stress with GRACE, Water Resour. Res., 51,
5217–5238, doi:10.1002/ 2015WR017349.
5. Food and Agriculture Organization, AQUASTAT data. Philippines - Renewable internal
freshwater resources per capita (cubic meters). Indexmundi. Retrieved from
https://www.indexmundi.com/facts/philippines/indicator/ER.H2O.INTR.PC?fbclid=IwAR1ZQ9sO
FF8HbmK_psCsdXiJTygzvyc_w9MjNUE2IBaGJz4cWTgte_c17Zc
6. Gultiano S., Balbarino E., Saz E., & Urich P. (2003). Geography of the Philippines”, Population
Dynamics, Land Availability and Adapting Land Tenure Systems : Philippines, a case Study, Office
of Population Studies (University of San Carlos), Farm and Agriculture Resource Management
Institute and Center for Social Research (Leyte State University. (coord.), Paris, CICRED, FAO,
2003, p. 29-57
7. ABS-CBN News. (2017). 2.1B People Lack Access to Safe Drinking water at Home: Report.
Retrieved from https://news.abs-cbn.com/overseas/07/17/17/21b-people-lack-access-to-safe-
drinking-water-at-home-report
8. Philippine Premier. (2016). Expat Guide: Is it Okay to Drink Water from Tap?. Retrieved from
http://primer.com.ph/tips-guides/2016/01/14/expat-guide-is-it-okay-to-drink-water-from-tap/
9. Asian Development Bank. (2015). Poverty in the Philippines. Retrieved from
https://www.adb.org/countries/philippines/poverty
10. Duffus, J.H. (2002). “Heavy metals a meaningless term?” Journal of Pure and Applied Chemistry,
74: 793-807.
11. Hawkes, S.J. (1997).“What Is a Heavy Metal?” Journal of Chemical Education, 74: 1374.

12. McCally, M.(2002) : Human and Heavy Metal Exposure. The Environment and Human Health. Ch.
4
13. Quintas, J. September 04, (2017) : Mining Industry in the Philippines. Manila Times. Retrieved
from http://manilatimes.net/mining-industry-philippines/348610/
14. Narvaez, D. (2002). Human Exposure to Mercury in Fish in Mining Areas in the Philippines.
FAO/WHO Global Forum of Food Safety Regulators Marrakech, Morrocco, 28-30. Retrieved from
http://www.fao.org/3/ab417e/ab417e.htm
15. Orbeta, Aniceto C., Israel, Danilo C., Asirot, & Jasminda (2000) : Mercury Pollution Due to Small-
Scale Gold Mining in the Philippines: An Economic Analysis, PIDS Discussion Paper Series, No.
2000-06
Kenneth John Anthony D. Tabag April 22, 2019

16. Tchounwou, P. B., Yedjou, C. G., Patlolla, A. K., & Sutton, D. J. (2012). Heavy metal toxicity and
the environment. Experientia supplementum (2012), 101, 133–164. doi:10.1007/978-3-7643-
8340-4_6
17. Akagi, H., Castillob, E., Cortes-Maramba, N., Francisco-Rivera, A., & Timbang, T. (2000). Health
assessment for mercury exposure among schoolchildren residing near a gold processing and
refining plant in Apokon, Tagum, Davao del Norte, Philippines. The Science of the Total
Environment 259 (2000) 31-43.
18. Drascha, G., Bose-O’Reilly, S., Beinhoff, C,. Roider, & G,. Maydla, S,. (2000). The Mt. Diwata
study on the Philippines 1999 assessing mercury intoxication of the population by small scale
gold mining. The Science of the Total Environment 267 (2001) 151-168
19. Hesperian Health Guides. (2016). A Community Guide to Environmental Health. Mining and
Health. Heavy Metals. Chapter 21. Retrieved from
http://en.hesperian.org/hhg/A_Community_Guide_to_Health:Heavy_Metals:_Mining_and_Heal
th
20. Morgan, H., De Búrca, R., Martin, I., & Jeffries, J., (2009). Soil Guideline Values for mercury in
soil. Using Science to Create a Better Place. Environmental Agency (2009) 1-10.
21. CBC News. (2014). Tailings ponds for mining and oilsands waste. Science and Technology.
Retrieved from https://www.cbc.ca/news/technology/tailings-ponds-for-mining-and-oilsands-
waste-faqs-1.2727889?fbclid=IwAR3tWypXwyZp3Gh4xwM9pC-rGCdnRjUF_gcPC96gtoCKjMB-
dpIlMSf3hGQ
22. World Health Organization. (2018). Lead Poisoning and Health. Retrieved from
https://www.who.int/news-room/fact-sheets/detail/lead-poisoning-and-health
23. World Health Organization. (2017). Mercury and Health. Retrieved from
https://www.who.int/news-room/fact-sheets/detail/mercury-and-health
24. Mollah, M., Schennach, R., Parga, J. & Cocke, D. (2001).Electrocoagulation (EC) Science and
Applications. Journal of Hazardous Materials, 84: 29-41.
25. Alguacil, F. (2003).A kinetic Study of Cadmium (II) Adsorption on Lewatit TP260 Resin.Journal of
Chemical Research, 3: 144-146.
26. Lalmi, A., Bouhidel, K., Sahraoui, B., & Anfif, C. (2018). Removal of Lead from Polluted waters
using ion Exchange Resin with Ca(NO3)2 for elution. Laboratory of Chemistry and Environmental
Chemistry LCEE. Hydrometallurgy Volume 178, June 2018, Pages 287-293. Retrieved from
https://www.sciencedirect.com/science/article/abs/pii/S0304386X1730573X
27. Babel, S. & Kuraniwan T. (2003). Low- cost Adsorbents for Heavy Metals Uptake from
Contaminated Water. Journal of Hazardous Materials, 1: 219-243.
28. Strathmann, H. (2001). Membrane Separation Process. Current relevance and future
Opportunities. Aicle journal, 47: 1077-1087.
29. Amado, R., Rodrigues, M., Morisso, F., Bernardes, A., Ferreira, Z. & Ferreira, C. (2008). High
Impact Polystyrene Membranes for Acid Solution Treatment by Electrodialysis: Preparation
Evaluation and Calculation. Journal of Colloid and Interface Science 320 (2008) 52–61.
30. Elmidaoui, A., Elhannouni, F., MenkouchiSahli, M., Chay, L., Elabbassi, H., Hafsi, M. & Largeteau,
D. (2001). Pollution of nitrate in Moroccan ground water: removal by electro-dialysis.
Desalination, 1: 325-332.
Kenneth John Anthony D. Tabag April 22, 2019

31. Emamjomeh, M. & Sivakumar, M. (2009). Review of Pollutants Removed by Electrocoagulation.

Journal of Environmental Management, 5: 1663-1679.
32. Chaudhari, A., Nagpurkar, L. & Ekhe, J. (2003). Up take of Heavy Metal Ions by Carbonaceous
Material obtained from Industrial waste Lignin using Microwave Irradiation. Asian Journal of
Chemistry, 15: 917-924.
33. Abdel, N., Hefny, M. & Chaghaby, G. (2007).Removal of Lead from Aqueous Solution using Low
Cost Abundantly Available Adsorbents. International Journal of Environmental Science
Technology, 1: 67-73.
34. Hong, J., Kim, J. & Choi, J. (2002).Hapten Synthesis and Influence of Coating Ligands on Enzyme -
linked Immune Reaction of ddt. Bulletin-Korean Chemical Society, 10: 1413–1419.
35. Satya, V. Y. Sridevil, V & Chandana , M.V.V. (2012). Adsorption of Heavy Metals from Aqueous
Solution. Environmental Science, 2: 1585-1593.
36. Hui, K., Chao, C. & Kot, S. (2009). Removal of Mixed Heavy Metal ions in Wastewater by Zeolite
4a and Residual Products from Recycled Coal fly Ash. Journal of Hazardous Materials, 27: 89-
101.
37. Cederberg, G. A., Street, R. L. & Leckie, J. O. (1985). A Ground Water Mass Transport and
Equilibrium Chemistry Model for Multicomponent Systems. Water Resource, 21:1095-1104.
38. Singh, V., Tiwari, S., Sharma, A. K.& Sanghi, R. (2007). Removal of Lead from Aqueous Solutions
using Cassia grandis Seed Gum-graft-poly (mehtylmethacrylate). Journal of Colloid and Interface
Science, 316: 224.
39. Gerpacio, R. V., J. D. Labios, R. V. Labios, E. & Diangkinay, I. (2004). Maize in the Philippines:
Production Systems, Constraints, and Research Priorities. Mexico, D.F.: CIMMYT.
40. Tin Win, D. (2005).Furfural-Gold from garbage. AU Journal of Technology, 8:185- 190.
41. Kramer Industry. (2018). Corn Cob Grit. Retrieved from
https://www.kramerindustriesonline.com/product/corn-cob-grit/
42. Fang Zhen. (1993). Physical and Chemical Properties of Corncob for Thermal Conversions, Fuel
Science and Technology International, 11:8, 1037-1045, DOI: 10.1080/08843759308916115
43. Sevilla, M., Fuertes, A.B., Mokaya, R.: Preparation and Hydrogen Storage Capacity of Highly
Porous Activated Carbon Materials Derived from Polythiophene. Int. J. Hydrog. Energy 36,
15658–15663 (2011).
Kenneth John Anthony D. Tabag April 22, 2019