Monday Research CHAPTER ONE
Monday Research CHAPTER ONE
Monday Research CHAPTER ONE
INTRODUCTION
The dramatic increase in Public awareness and concern about the state of the global and
Local environments which has occurred in recent decades, has been accompanied and partly
prompted by an ever-growing body of evidence on the extent at which pollution has caused
The introduction of harmful substances into the environment has been shown to have much
adverse effect on human health, agricultural productivity and natural ecosystems. Soils may
from the rapidly expanding industrial areas, mine tailings, disposal of high metal wastes,
leaded gasoline and paints, land application of fertilizer, animal manures, sewage sludge,
pesticides, waste water irrigation, coal combustion residues, spillage of petrochemicals and
atmospheric deposition, Garbanno, et al.,1995. Some heavy metals like arsenic, cadmium and
lead have been reported to have no known bio-importance in human and physical and
consumption even at very low concentrations can be toxic, EU, 2012, Nolan, 2003. To a
small extent, trace metals enter the body system through food, air and water and bio
This study investigates the level of selected heavy metals in soil samples within the vicinity
of tin mines area in Alhamis, Mada Station and Arikpa Areas of Nasarawa Eggon Local
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1.1 STATEMENT OF PROBLEM
In recent years, concern over the impossible effects of the increasing accumulation of
metallic contaminations in the environment is growing. Yahaya et al., 2009. For this reason,
the investigation of heavy metals in soil is essential since slight changes in their concentration
above the acceptable levels whether due to natural or anthropogenic factors can result in
serious environmental and subsequent health problems, Fanqueiro et al., 2004. The situation
of heavy metals pollution is more worrisome if the developing countries where research
effort toward monitoring the environment have not been given the desired attention by the
stake holder, (Yahaya et al., 2009. In Nigeria the situation is no better by the activities of
most industries and populace towards mining activities and management which usually lead
The aim of the study is to determine the concentration of heavy metals on the overburden and
non-mining soil samples taken from mining areas within Nasarawa state,
To compare the concentration of the selected heavy metals between the mining and
non-mining vicinities of Alhamis, Mada Station and Arikpa Areas of Nasarawa Eggon
To compare the results with WHO standard limits and to determine possible sources
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1.4 JUSTIFICATION OF STUDY
Research have been carried out on heavy metals determination in soil within mining areas
and have all indicated that heavy metals are present at different concentrations and in various
forms in the polluted and unpolluted soils. These metals affect lives, environment and plant
productivity if they are found exceeding the WHO (World Health Organization) standard for
regular intake. The results obtained in this research will create awareness as to the status of
The scope of this study involves the determination and comparison of the heavy metal’s
concentration on mining and non-mining soil. This research will provide database for risk
evaluation of metals levels of soil in Alhamis, Mada Station and Arikpa of Nasarawa Eggon
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CHAPTER TWO
Several studies (research work) has been carried out on trace metal determination in soil
within mining areas, and have all indicated that trace metals or heavy metals such as Cd, Cu,
Zn, Hg, Pb are present at different concentrations and in various forms in the polluted and
unpolluted soils. The most important sources of heavy metals in the environment are the
anthropogenic activities such as mining, smelting procedures, steel and iron industry,
chemical industry, traffic, agricultural as well as domestic activities, Suciu et al., 2008,
Chopin et al., 2007; Stihi et al., 2006. Chemical and metallurgical industries are the most
important sources of heavy metals in soil, Panelica et al., 2008, Cojocanu et al., 2006. The
presence of heavy metals in soil can affect the quality of food, ground water, micro-organism
activity, plant growth e.t.c., Devries et al., 2007, Popescu et al., 2009.
Musa and Jiya (2011), and Olaniyan (2008) revealed that the indiscriminate mining on the
Jos Plateau led to many parts of the area being exposed to erosion and reduces the availability
of land for crop production. The volume of mineral tripped off during mining reduces the
Nassarawa Eggon Local Government Area is an extensively mined area, which was
dominated by use of heavy earth moving equipment and draglines. As a result, the zone is
characterized by deep excavations and dumping of high overburden, mine ponds, mine tailing
According Gyang and Ashano (2010), the major problem of the area still remains the
devastated and de-vegetated land and mine spoils depriving the inhabitants of fertile farm
land Lavis (2011) explained that the deep mining which is an excavation of underlying sand
has created mining pits, man-made lakes, pools and ponds which have great effect on both
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the people and agricultural practices. Mining ponds have always been death traps for people
and animals.
Olaniyan (2008) reported that the area extents of devastated arable land by open-cast tin
mining is estimated at 316km2, which comprises of mine spoiled soil (overburden), pits
paddocks site of abandoned equipment’s mining scars tailing mine dumps and ponds,
Balogun (2007) pointed out that the Jos mining region covers an area of approximately
3,670km2 about 43% of the total area of Jos Plateau. As a result of intensive mining activities,
the area is badly dissected by erosion gulies mined ponds and dumps. The original wood and
vegetation of the Jos region has long been cleared for mining and agricultural activities,
turning the region into one savannah grassland with widely spread eucalyptus and acacia
trees, and cactus hedges which are used for land boundary delineation.
Wahla and Kirkham (2008) reviewed that Nickel, lead and mercury are the micro nutrient
essentially for the soil. They occur naturally in the plant and animal tissue. They are required
in only very small amount, if plants are supplied to these heavy metals more than they
required, it will lead to toxicity in them and ultimately death. The usually routes by which
human received exposure to these heavy metals are through skin or eye contact, as well as
Murray et al., (2004) pointed out that the natural and anthropogenically introduced
concentrations of metals in the near-surface soil can vary significantly due to different
physical and chemical processes operating within soils across geographical regions.
Migration of metals in the soil is influenced by physical and chemical characteristics of each
specific metal and by several environmental factors. The most significant environmental
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i. Soil type
iv. pH
Chaney et al., (2008) reviewed that one of the greatest concerns for human health is caused
by lead (Pb) contamination. Exposure to Pb can occur through multiple pathways, including
inhalation of air and ingestion of Pb in food, water, soil or dust. Excessive Pb can cause
seizures, mental retardation and behavioural disorders. The dangers of Pb is aggravated low
Elinder (2005) revealed that however, immobilized cadmium is available to plant life and can
easily enter the food supply. Cadmium in soil tends to be more available when the soil pH is
low (acidic). In surface water and ground water, cadmium can exist as hydrated ion or as
ionic complexes with other inorganic or organic substances. While soluble forms may
sediments. Cadmium is taken up and retained by aquatic and terrestrial plants and is
concentrated in the liver and kidney of animal and plants. Water sources near cadmium –
emitting industries, both historic and current operations have shown a marked elevation of
cadmium in water sediments and aquatic organism, Amason and Fletcher 2009; Mason et al.,
2006.
In general, vegetables particularly leafy vegetables such as lettuce (0.051mg/kg) and spinach
all vegetables ranged for 0.001 to 0.124mg/kg, FDA, 2010, Morrow, 2005. Peanuts,
soybeans, and sunflower seeds have naturally high levels of cadmium, Morros 2005; the
mean concentration of cadmium in legumes and nuts ranged from 0.001 to 0.054/kg, FDA,
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2010. Excessive levels of cadmium in food can have implications for human health and in
Kramer et al., (2007) discussed that, micronutrient such as Zn, concentrations of these ions
can be toxic. Commonly Mn, Ni and Cu are essential for plant growth and development; high
intracellular accumulator plants have evolved several mechanism to control the homeostasis
of intracellular ions such mechanism include regulation of ion flux (Stimulation of transporter
activity at low intracellular ion supply and inhibition at high concentrations) and extrusion of
intracellular ions back into the external solution. Metal hyper accumulator species, capable of
Davis and White (2010) reported that the concentration of the cadmium and zinc in
vegetables grown on soils contaminated by the base metal mining varies by (<0.05 to
D’ Amore et al., (2005) affirmed that the inability to determine metal species in soils
hampers efforts to understand the mobility, bioavailability and fate of contaminant metals in
environmental systems together with the assessment of the health risks posed by them, and
the development of methods to remediate metal contaminated sites. However, in some natural
soils developed from metal rich parent materials, as well as in contaminated soils, up to 30 to
Francek (2008) investigated soil lead levels in small environment using A.A.S technique 1g
of the sieved soil samples were digested with a 1:1 HNO 3 solution, evaporated to dryness on
a hot plate and cooled. The procedure was repeated with 1:1 HCl solution. Extracts were
filtered and added to distilled water total 25ml and analyzed using A.A.S technique.
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Sovory et al., (2007) determined chromium in biological materials. The Cr present was
converted to trifluoroacetate, extracted into benzene and determined by electron capture has
chromatography.
and proposed the use of (NH4)2 SO4 as a soil additive to provide nutrient (N and S) needed for
high yield and to acidify the soil for greater metal bioavailability. It should be noted that there
may be some negative side effects associated with soil acidification. Take for instance due to
increased solubility some toxic metal may leach into the ground water creating an additional
soil could be limed to elevate the PH near a neutral value premature liming may increase soil
capacity for metal binding and restrict the potential for phyto-extraction. A similar effect can
be expected following the addition of organic fertilizers. In addition, the raising of pH may
stimulate the formation of metal hydroxyl ions, such as ZnOH+, which is more strongly
sorbed soil solids than the uncomplexed ions. Phosphorus is major nutrient, and plants
production. The addition of phosphorus fertilizer, however, can also inhibit the uptake of
some major metal contaminants, such as Pb, due to metal precipitation such as pyromorphites
and chloropyromorphites.
Aziz et al., (2004) confirmed that industries such as planting, ceramics, glass mining and
battery manufacture are considered the main sources of heavy metals in local water systems
causing the contamination of ground water with heavy metals. Heavy metals which are
commonly found in high concentration landfill leachate are also a potential source of
pollution of ground water. Large areas of agricultural land are countermined by heavy metals
that mainly originate form farmer or current mining activities, industrial missions or the
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Egila and Nimyel (2002) reported for variation in heavy metal concentration in the sediment
of some dams in Plateau State. Among the metals detected. Pb has the lowest concentration
and the concentration was higher during the dry season for the two years, this way be as a
result of efficient sedimentation since the water is only disturbed by tidal current during the
dry season all the metals examined are below the world health organization (1993) standard
but the dams should be closely monitored since there is usually slight increase in the
Appel and Ma (2007) state that the overall behavior of heavy metals in soil is said to be
governed largely by their sorption and desorption reactions with different soil constitution,
especially clay components. The chemical behavior of heavy metals in soils controlled by a
number of processes, including metal action realize from contamination source materials (e.g
fertilizer, sludge, smelter, dust, ammunition, sag) cation exchange and specific adsorption to
surface of minerals and soil organism matter, and precipitation of secondary minerals.
El-ghawi et al., (2008) studied the trace metal contaminations in some Libyan soils and found
that the concentration of clay surface soil is higher than in sandy soil. The multiple regression
analysis performed confirmed the importance of pH as well as other soil properties such as
texture electrical conductivity and organic matter or carbonates on the behavior of nutrient
Egila et al., (2010) reported the effect of pH can heavy metal adsorption from aqueous
solutions. It was found that removal of heavy metals ions was P H dependents. For his reason,
the pH solutions were varied from 1 to 10 for the three investigated metal ions. It is clear that
Pb (II) ion was effectively absorbed in the pH range 4,5 and 6 with the highest percentage
removal is at pH while for cadmium (II) ion and cobalt (II) ion, maximum removal also
occurred t pH 6. The increase in the amount of metal ion adsorbed due to the increase in pH
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may be explained on the basis of a decrease in competition between proton (H +) and the
posted charged metal ion at the surface sites and by decrease in positive charge near surface
Filep (2008) stated that contaminants reaching the soil can be divided into two groups namely
molecules, which are toxic at very low concentration. Macro-pollutants are present in the
environment locally and or temporarily to a much higher degree than normal level. The main
micro pollutants of the inorganic micro-pollutants are mainly the toxic and potentials toxic
heavy metals (Pb, Cd, Ni Cr, Hg, Cu, Zn e.t.c.) while the organic micro-pollutants includes
pesticides and certain non-pesticides organic molecules; e.g aliphatic solvents, monocyclic
Khan (2005) reviewed that metal such as lead, arsenic, cadmium, copper, zinc, Nickel and
mercury are continuously being added to our soils through various agricultural activities such
as agrochemical usage and long-term application of urban sewage sludge in agricultural soil
industrial activities such as waste dispersal, waste incinerator and vehicle exhausts, together
with anthropogenic source. All these sources cause accumulation of metals and metalloids in
our agricultural soils and pose threats to food safety issues and potential health risks due to
El-qhawi et al., (2005) shows that trace metals concentrations in clay surface soils are higher
than in the sandy soils, humic and folic acid (organic matter) capture the elements. Heavy
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metals cations absorb to soil organic matter and other forms of humified natural organic
matter.
Carolna et al., (2007) stated that heavy metals in soil samples can be determined by highly
sensitive spectroscopic techniques such as atomic absorption spectroscopy (e.g flame atomic
absorption spectroscopy (FAAS) and graphite furnace atomic absorption spectrometry (GF
AAS) and inductively coupled Plasma (ICP) spectrometry (e.g KP atomic emission
These techniques require the transformation of a solid sample into solution from which metal
concentrations are determined. They also mentioned that heavy metals in soil samples are
The most important methods used for soil digestion consist of open vessel digestive by
digester block and closed vessel digest by micro wave over. Given that it is well known that
different digestion methods may lead to different result, a validation process is needed to
demonstrate data quality and select the most useful method according to the characteristics of
the study area and particularly soil properties. Result obtained applying theses digestion
methods are generally use to assess the degree of pollution in soil. Therefore, the choice of
the digestion method has to be suitable in order to provide information on the total content of
Slagle et al., (2004) measured the concentration of ten trace elements (AS, Ba, Cd, Cr, Cu,
Mn, Ni, Pb, Se, Zn) which were determined by inductively coupled plasma-atomic emission
spectroscopy (ICOAES) after microwave digestion by USEPA method 305, and HF method.
Trace element concentrations using USEPA 3051 were about 1.5 to 5 times lower than the
amounts extracted by the HF method, except for Mn, method 3051 of the USEPA used
concentrated HNO3 acid following solid waste procedure SW 846-3051 (S.U EPA 2007).
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This method involved a closed vessel using pressure and temperature-controlled microwave
heating for dissolution. The HF method used a combination of three concentration acids;
HNO3, HF and HCl with microwave digestion. The HF and HCl with Microwave digestion.
HF method should represent a “total” quality of trace elements present in the soil because
concentrated HNO3, HF and HCl acids cause soil components to dissolve, thereby releasing
Chen et al., (2009) made a comparison of EPA method 3050 (hot-plate, HNO3-HCl), 3051
was thus conducted by digesting three Nist standard reference materials (SRIMS) and 40
representative florida surface soils. Fifteen trace metals (Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn,
No, Ni, Pb, Sb, Se, and Zn) and six elements (Al, Ca, Fem K, Mg and P) were analyzed using
and inductively coupled plasma spectrometer (ICP) or an inductively coupled plasma mass
spectrometer (ICP-MS) except for As, Cd, Pb, and Hg, which were analyzed either by a
concentrations of most trace metals in florida soils are primary controlled by soil properties.
The most effective and useful digestive method to be applied to agricultural soils devoted to
growing vegetable crop is open vessel digestion using a digester block with HNO 3, HClO4,
HCl and microwave assisted digestion using HNO 3, and HCl (Carolina et al., 2007). In site
immobilization is a promising approach that has the potential to remove metals from
designates a group of elements that occur in natural systems in low concentrations. It can also
be defined as elements used by organisms in small quantities but are believed to be essentials
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to their nutrition, Adriano, 2001. The trace elements in soils are derived from both parents’
The occurrence of heavy metals in soil can be geogenic or natural and anthropogenic origins.
It occurs naturally in the soil environment from the pedogenetic processes of weathering of
parents at levels that are regarded as (<1000mgkg-1) and rarely toxic, Kabata Pendis, 2001.
Due to the disturbance and acceleration of natures, slowly occurring geochemical cycle of
metals above by man, most soils of rural and urban environment may accumulate one or more
of the heavy metals above defined background values, high enough to cause ricks to human
health, plants, animals, ecosystem or other media, Amore et al., 2005. The anthropogenic
sources include mining, smelting fossil fuel combustion and various industrial activities,
Adekola et al., 2012. Industrial activities are the major sources of soil heavy metals
contamination, Chandia et al., 2005, Chen et al., 2005 Fayun et al., 2008 Olajire 200s. some
trace elements including Cn, Zn, Mn, Fe and Mo and B are essential for plant growth and are
called micronutrient, except for B, these elements such as Co and Se are not essential to plant
growth but are required by animals and humans. Other trace elements such as Cd, Pb, Cr, Ni
and Hg have toxic effects on living organism and are often considered as contaminants. Soil
contaminations by trace elements derived from parent materials or point sources often occur
in limited areas., the trace metals of soil are highly dependent on the rocks from which the
soil parent materials was derived and on the process of weathering that the soil forming
materials have been subjected, thus the older the soil the less likely is influence of parent
rocks, Adriano, 2001. Normal concentrations of some trace metals in soils as well as
concentrations at which these elements become toxic, Ross, 2004 is as shown below:
Elements normal range in soil (total) (μ Concentration in soil considered toxic ( μ gg-1
Cr 5-1000 75-100
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Mn 200-2000 1500-3000
Co 1-70 25-50
Ni 10-1000 100
Cu 2-100 60-125
Zn 10-300 70-400
Cd 0.01-7 3-8
Sn <5 50
Hg 0.02-0.2 0.3-5
Pb 2-200 100-400
Cadmium a rare but widely dispersed element, is found naturally in the environment. Most
Cadmium sulphide
It is released into the environment through manning and smelting, its use in various
industrials processes and enters food chain from uptake by plants from contaminated oil or
water. Apart from mining and smelting, other man – made routes include;
Presence in sewage sludge and various industrial uses such as Nicd batteries, plating
pigments and plastics. ATSDR, 2005. While the natural sources include underlying
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bedrock or transported parent materials such as glacial till alluvium, EPA, 2010;
Lenntech.com, 2008.
Cadmium occurs in the carth’s crust at an abundance of 0.1-0. 5ppm and is commonly
associated with zinc, lead and copper ores. It is also constituent of ocean water with average
level between <5 and 110mg/l: with higher levels reported near coastal areas and in marine
Cadmium can be released to the atmosphere through metal production activities, fossil fuel
combustion and waste incineration. The main cadmium compounds found in air are cadmium
coxide, chloride and sulphate and these compounds are expected to undergo minimal
transformation in the atmosphere, EPA, 2008. The major fate of cadmium is air through
transport and decomposition. Cadmium can travel long distance in the atmosphere and then
pesotie (wet or dry) into surface soil and water, which can in elevated cadmium levels even in
remote locations, Shevchenko et al., 2007. The main sources of cadmium to soil include
atmosphere deposition and direct application methods such as phosphate fertilizer use and
sewage sludge disposal. Some phosphate fertilizer can contain up to 300mgcd/kg, Alloy way
and Steinned, 2009. cadmium mobility in soil and the availability of organic matter.
Generally, cadmium will bind strongly to organic matter and this will for the most part,
Lead is the heaviest of the non-radioactive metals that naturally occurs in substantial qualities
in the earth surface. Lead is a soft, malleable ad stable metal, which is often used in the
manufacturing of storage batteries. Lead is present in all soils, rivers, lakes, and sea water via
the process of smelting, mining and refining. Despite it’s weight lead is also in the air, a
component of dust and of sea spray. Natural soils usually have less than 50ppm of level but
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are never lead free. Lead is present in all proportion of 16ppm in igneous rocks, and at an
average of about 10ppm in common soils that are far from sites of contamination. The main
health problems associated with chronic high levels of lead in blood and neurological
Copper is a trace element that is essential for most animals, including humans. The influence
of copper upon human health is due to the fact that it is part of enzymes, which aids proteins
that help biochemical reactions occur in every cell. Copper 1 involved in the absorption, stage
and metabolism of iron, copper may be absorbed by both the small intestine and mucosa,
with most absorbed by the small intestine. Copper is found in the blood bound to proteins.
Klevay and Medeires 2006. Copper is utilized by most cells as a component of enzymes
involve in energy production (Cytochrome Oxidase) and in the protection of cells from free
radical damage. It is also involved with enzymes involved in energy production and in brain
of the proteins ceruloplasmin transport copper as well as helps convert iron to form that can
be transported to other tissues, Medeiros and Wildman, 2007. Cases of copper toxicity are
rare but may occur; excess copper consumption may lead to liver damages. Intake of
supplements exceeding 3mg copper per day for a protected period of time may cause for
concern. Doses of long per day over several weeks may lead to toxic symptoms, such as
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2.1.4 Chromium (Cr)
This is a trace metal that exits in several forms. The forms in which chromium existence:
a. Chromium (III)
b. Chromium (IV)
People can be exposed to chromium through breathing, cating or drinking and through skin
contact with chromium compounds. The levels of chromium in air and water are generally
low. In drinking water, the level of chromium 1 usually is low as well as but contaminated
well water may contain dangerous chromium (IV). For most people eating food that contains
chromium III is the main raute of chromium uptake, as chromium (III) occurs naturally in
man vegetables, fruits, meat, yeats and grains, Douson and Velazuez, 2006.
The toxic effect of chromium (III) as a result of chromium (III) deficiency are disruptions of
metabolism and diabetes while excess uptake of chromium (III) cause skin rashes. Chromium
(VI) is a danger to human health, mainly for people who work in the steel industry, people
who smoke tobacco also have a higher chance of exposure to chromium. The toxicity of
chromium (VI) results into the following health problems, skin rashes, pushes, upset stomach,
respiratory problems, weakened immune systems, kidney and liver damage, alteration of
genetic materials, lung cancer amongst others, Lindberg and Herdensteir Na, 2007.
Mercury is a heavy metal belonging to the transition series of the periodic table. Mercury is
widely spread on the environment as toxicant and [pollutant which induces severe alterations
in the body tissues and causes wide range of adverse effect on health. Both humans and
animal are exposed to various forms of mercury vapor (Hg0) organic mercury (Hg 1+),
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mercuric (Hg2+) and the organic mercury compounds. Because mercury is ubiquitous in the
environment, humans, plants and animals are all unable to avoid exposure to some form of
mercury.
Nickel (Ni) is the 24th most abundant element in the Earths crust, comprising about 3% of the
composition of the earth and is present in the air, water, soil and biological material (Cempel
and Nikel, 2005). Nickel is one of many trace metals widely distributed in the environment,
being released from both natural and anthropogenic activity (Cempel and Nikel, 2005). Most
of the Nickel in the human body originates from drinking water and food (Cempel and Nikel,
occupational pollutant.
Zinc is an element of moderate abundance in the earth crust and the presence of zinc in the
environment is associated with mining and smelting which pollutes the air, water and soil
with fine particles (Tiimub et al., 2015). Zinc is an essential mineral that is naturally present
2.2 OVERBURDEN
Overburden (also called spoiled) is the materials that lies above an area that lends itself to
economical exploitation, such as the rock, soil and ecosystem that lies above the ore body.
Overburden is distinct from tailings, the materials that remains after mining of valuable
component have been extracted from the general finely milled ore. Overburden is removed
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