A STUDY ON SELECTED HEAVY METAL CONTAMINATION IN

INDUSTRIAL SOILS OF VISAKHAPATNAM

A Project report submitted in partial fulfillment

For award of the Degree
of

BACHELOR OF ENVIRONMENTAL MANAGEMENT

by
J. BEULAH MADHURI M.ROHINI JYOTSNA R.KUSUMA PRIYA
(REG NO: 1212216106) (REG NO: 1212216111) (REG NO: 1212216116)

Under the Guidance

of

Dr. PADMAVATHI BANDARU

Assistant professor

DEPARTMENT OF ENVIRONMENTAL STUDIES

INSTITUTE OF SCIENCE
GITAM (DEEMED TO BE UNIVERSITY)
VISAKHAPATNAM-530045
2018-2019
 CERTIFICATE

This is to certify that the Project Work entitled “A STUDY ON SELECTED HEAVY METAL
CONTAMINATION IN INDUSTRIAL SOILS OF VISAKHAPATNAM” has been carried
out by J Beulah Madhuri, M. Rohini Jyotsna, R. Kusuma Priya towards the partial
fulfillment for the award of the degree in Bachelor of environmental Management (B.E.M.),
GITAM Institute of Science, GITAM (Deemed to be University) under my supervision and
guidance during the year of (2018-2019).

Dr. Padmavathi Bandaru

Assistant Professor

Prof. N. SRINIVAS Examiner’s signature

Head of the Department

GITAM Institute of Science

GITAM (Deemed to be University)

Visakhapatnam -45.
 ACKNOWLEDGEMENTS

It is our deep gratitude and sincere thanks to our guide Dr. Padmavathi Bandaru, Assistant
Professor, Department of Environmental Studies, Institute of science, GITAM (deemed to be
university), Visakhapatnam, whose co-operation and amicability helped us to complete our
project successfully.

We are grateful to Prof. N .Srinivas, Head of the Department of Environmental studies, Institute
of science, GITAM (Deemed to be university), Visakhapatnam who gave us an opportunity to do
this work, which will be a priceless asset for my career.

We take privilege in extending our deep sense of gratitude to Prof. Ch. Ramakrishna Director,
UGC Affairs and Research Activities, GITAM (Deemed to be university) for extending support
to carry out our project work successfully.

We OWE our thanks to Smt. A. Gayathri, Lab Assistant for her constant co-operation for smooth
execution of the experimental work, we extend our thanks to Mr. G.Venkat rao, Lab attender for
all the possible help rendered throughout this project, and thanks to Mr. Bh. Sathish Kumar,
Junior Assistant for his support.

Finally, we express our heartfelt gratitude to our parents and our well wishers who have been
encouraging us throughout. We also thank our friends who have been so supportive during our
work.

J. B. Madhuri M. R. Jyotsna R. Kusuma Priya

ABSTRACT:

Heavy metals are natural constituents of earth crust and are essential for the metabolic
activities in biotic components. Even though the industrial and occupational sectors buildup the
economy, it also triggers the various health effects due to metal contamination. Mostly
anthropogenic deposition may possibly increase heavy metal concentration in the soil system. Its
toxicity at higher concentration has become the major concern of the world today.

The present study focuses on the estimation of heavy metals namely Cr (VI) and Ni (II)
present in selected soil samples in and around industrial area located near Atchutapuram,
Visakhapatnam. Initially acid digestion was carried out with the soil samples using a standard
digestion method. Using millipore water and analytical grade reagents, metal concentrations
were determined spectrophotometrically.

Cr (VI) was found to be in the range of 0.8 mg/kg – 3 mg/kg where as Ni (II) was in the
range of 5 to 17.4 mg/kg within the samples collected from industrial area. Slight variations
were noticed from the soil samples collected from the residential areas near to the industrial area.
The soil parameters namely pH, EC, Organic Matter were also estimated as they influence the
availability of metals in the soil. It is significant to check the fate of heavy metals in the
environment due to their toxicity at higher concentrations.

Key words: Heavy metals, Cr (VI), Nickel (II), soil parameters.

 INDEX
S.NO CHAPTER Page no.

1 INTRODUCTION
1.1 Sources of heavy metals

1.2 Entry of chromium and nickel into soil

1.2.1 Chromium

1.2.2 Nickel

1.3 Effects of heavy metals on environment.

2 SCOPE OF WORK

3 REVIEW OF THE LITERATURE

4 MATERIALS AND METHODOLOGY

5 RESULT AND DISCUSSION

6 CONCLUSION

7 REFERENCES
INTRODUCTION
Soil, is simply spelled out as “the Skin of the Earth”. Soil covering the Earth is maintained as
medium for plant growth and storage of water. Land degradation has become a major problem,
due to rapid industrial development that has taken in many parts of the world especially in
rapidly developing countries like India [Shiva Kumar et al., 2014]. Due to many anthropogenic
activities, the soils surrounding the industrial areas may be polluted leading to heavy metal
contamination [Alpa varsani and kapila manoj 2015].

The pollutants are getting deposited on the soil from various domestic and industrial sectors. The
soils get accumulated by toxic substances such as metals, trace elements and other organic
substances (Rakesh Sharma and Raju, 2013). The heavy metal contamination may lead to
change in soil characteristics that may effect plant growth, food quality, productivity and
environmental quality[Pushpanjali,P.B tejaswi et.al,2017]. Continuous release of heavy metals
from anthropogenic sources causes serious change in biogeochemical cycle of those elements.
[Celine siu-lan lee, xiangdong li, et al, 2005] The toxic metals like Cd or Pb can easily penetrate
into the crops and can enter into the food chain [waalkes 2000, satarug et al 2003].

SOURCES OF HEAVY METAL POLLUTANTS:

The two main sources of heavy metals in soil .they are

 Natural
 Anthropogenic/human.

NATURAL SOURCES

Almost all metals present in the environment have been biogeochemical cycled since the
formation of the earth. The natural factors include soil erosion, volcanic activities, urban
runoffs and aerosols particulate. Naturally heavy metals and metalloids in soils are derived
from the soil parent material. [Brain j, alloway 2013] Direct processes such as escape of
gases and fluids along major fractures in the earth’s crust, can also provide significant
 sources of metals to surface environments, including the atmosphere and sea floor [Robert G.
Garrett, 2000].

ANTHROPOGENIC SOURCES

Sources of heavy metal pollution in environment are mainly borrowed

from anthropogenic, that constitute power plants, coal combustion, metallurgical industry,
chemicals plant, domestic emission, weathering of buildings and pavement surface and
atmospheric deposits. The pollutants are getting concentrated in agricultural soils by various
activities include mining, waste disposal, urban effluent, vehicle exhausts, sewage sludge,
extensive application of chemical pesticides, insecticides and fertilizers application.

Soil is treated as contaminated when chemicals are present or other variations have been
made to its natural environment. This is generally created by accidental releases of chemicals or
the irregular disposal of hazardous wastes. Increased inputs of metals and synthetic chemicals in
the terrestrial environment due to rapid industrialization coupled with inadequate environmental
management in the developing country like India has lead to environmental degradation (al-
khashmanoa .,2013,liz,fenz x, lig, et al 2013, zhang c, qiao q et al 2012).

ENTRY OF CHROMIUM AND NICKEL INTO THE SOIL:

CHROMIUM (Cr):

Chromium (Cr) is a d block transition metal with the atomic number of 24 and it is the
first element in group 6 of the periodic table. Chromium normally exhibits wide range of
oxidation states. The most common oxidation states of Cr in the soil are +3 and +6. Chromium is
odorless and tasteless.

Chromium is mainly used in metallurgy mainly to impart corrosion resistance, hardness

and shiny finish. It is also used in steel fabrication, manufacturing of stainless steel and alloys,
paint and pigment manufacturing and leather tanning.
CHEMICAL BEHAVIOUR OF CHROMIUM IN SOILS:

Mostly chromium exits in Cr (III) and Cr (VI) oxidation states. In terms of fate and chemical
behavior of Cr in soil there is a great contrast between Cr (III) and Cr (VI). Cr (III) hydroxide
has low solubility and strong retention on soil. Cr (III) limits the mobility and bioavailability in
soils. Chromium (VI) is a strong reducing agent and it is highly toxic to all living organisms and
plants [Zayed, A.M; Terry, N 2003].

Chromium (VI) as chromate is highly soluble in water and also acts as strong oxidizing agent
this makes chromium Cr (VI) a highly mobile element. In the presence of some reducing agent
Cr (VI) reduces to Cr (III), where this reduced Cr (III) can form into highly soluble organic
compounds in some acidic conditions [Avudainayagam; Megharaj, et al, 2003]

NICKEL (Ni):

Nickel (Ni) is a d block transition chemical element with the atomic number 28. Nickel lies in
group 10 in the periodic table. The oxidation state of nickel are +1, +2, +3 and +4 but among all
the oxidation states Ni (II) is the most stable oxidation state.

Normally Ni is mostly used in manufacturing of alloys and stainless steel. The alloys of nickel
are characterized by high strength, resistance to corrosion and heat, ductility. Nickel alloys are
also used in plating, minting coins, foundry, catalysts and rechargeable batteries. High
concentrations of nickel in soils have potential negative impact on both plants and animals
[Thakali S; Herbert, E.A; 2006]

CHEMICAL BEHAVIOR OF NICKEL IN SOIL:

Ni is more stable in aqueous solution. pH is the important factor which affects the
behavior of nickel in soils. The increase in mobility of Ni is indirectly proportional to pH and
cation exchange capacity. Some other factors such as water logging, addition of manures
(organic), and sewage sludge into the soil also can influence the fate and behavior of nickel in
soil. The physiochemical characteristics of soil influences bioavailability and mobility of nickel
in soil [Covelo, E,F.; Matias, J,M,;2008]. The mobility of Ni reduce when it precipitates [Mc
Near, Jr D.H chaney et al,2007]
EFFECTS OF HEAVY METALS ON ENVIRONMENT:

Heavy metals are hard elements that have high density. Heavy metal pollution is
mainly noticed in point source areas (mining, smelters, and other metal based industries) which
are mainly caused due to anthropogenic activities.

The most common metals present in contaminated sites are copper, zinc, lead, nickel, chromium
etc. Heavy metals also have capacity to reduce crop production. Toxic metals enter into living
organisms through bioaccumulation and biomagnification.

Chromium:

Less exposure of chromium to the body may irritate the skin and cause ulcers. Long term
exposure of chromium may cause damage to kidney, liver, nerves and circulatory system.
Chromium may also affect the plant growth and crop productivity. [Risco Taufik Achmad et al,
2017]

Nickel:

Nickel is an essential element in plants and many other biota, there as been much more concern
about the toxicity of nickel than about its deficiency. Therefore, prolong exposure to oxides and
sulfides of nickel is associated with possible risk to lung and nasal tumors, while systematic
effects whose initial symptoms are mild nausea, headache and chest pain[pawel harasim, Filipek
2015].

Higher concentrations nickel may cause skin irritation and decrease in body weight. Nickel also
damages liver and heart. Nickel can enter into the plant, animal, and human tissues through air
inhalation and manual handling.[Zambelli B,etal,2013]
OBJECTIVE
 Identification of polluted side in Visakhapatnam.

 To estimate the amount of Cr (VI) and Ni(II) present in the soils collected from

the industrial based soil.

 To estimate the soil parameter like Ph, Electrical conductivity and organic matter

Present in the soil.

 To identify the correlation between the selected metals and soil parameters.
SCOPE OF WORK
 It has been proved that the release of toxic chemicals from industries have become very
harmful to living organism and also to the environment. These chemicals when released directly
into the soil may also cause damage to the soil and its fertility. This ends up leading loss of crop
and crop yield.

Most of the chemicals released from industries are non-degradable .Therefore to make
environment free from toxic metals certain remedies are to been taken by the industrial sectors.
REVIEW OF THE LITERATURE
In year 2018 noucleng vongdala, hoang-dangtran et al, conducted a study on the accumulation of
heavy metals in soil and plants. The study stated that the villagers consumed the vegetables
where toxic heavy metals were accumulated. More than 70% of the soil is contaminated in the
sourrounding areas.

In year 2018, Nwankawoalaho and ememu R.J. studied heavy metal contamination in the soil
and groundwater. The level of heavy metals in soil can affect the quality of food groundwater,
microorganisms’ activity and plant growth etc.

Zhongping yang, wenxilu in year 2014 estimated heavymetals in urban and industrial soil they
stated that the areas in china are totally polluted with heavy metals.

In 2012 M.S.Daud and Odoh.R stated that mining, smelting industrial and the associated
activities are one of most important sources .By which soils, plants and surface waters are
contaminated.

R.K.Rattan, SP.datta in 2005 conducted experiment on heavy metals in soil , cropsand

groundwater. They stated that the vegetables are not likely to induce any health hazard to
consumers as far as its metal contents are concerned

In 2007 A .k. Krishna, P. k Govil reported about the pollution of soil by heavy metals and its
effects to environment as well as to the humans.

In 2015 Sujatha.B, Prasanna Kumar M.V.V Excessive deposition of heavy metals such as
mercury(Hg),Cadmium (Cd) , lead(Pb) , Chromium(Cr) , Arsenic(Ar) in the soil by human
activities which are highly hazardous to the environment and organisms.

In 2009, teodor velea, Liliana Gherghe, Vasile Predica reported about the heavy metal
contamination in vicinity of an industrial area, mainly about the background ,aim, scope of lead
and its effects to human health.

In 2015, Ruqia nazir, muslim khan .muhammad masab et al stated about the accumulation of
heavy metals such as Ni, Cu , Cd , Cr , Pb , Zn , Fe in soil ,water, plants and also described about
the physico-chemical parameters of soil and water.
In 2017,Pushpanjali,P.B. Tejaswi , K. L Sharma et al .,reported about the impact of industrial
pollution on soil quality and heavy metal contamination to crop field near to the industry.

In 2015,najir et al ., reported on accumulation of heavy metals (Ni, Cu, Cd, Cr, Zn, Fe)in the soil,
water and plants and analysis of physic-chemical parameters of soil and water of kohat, Pakistan.

In 2014, su et al, reported on heavy metal contamination in soil worldwide. The situation impact
and remediation techniques were also discussed. They compared and analyzed soil
contamination of heavy metals in various cites and countries. They also reviewed background,
impact and remediation methods of soil heavy metal contamination worldwide

In 2011 Adelekan and Abegunde reported on heavy metal contamination of soils and
groundwater stated that heavy metal pollution refers to cases where the quantities of these
elements in soils are higher than the maximum allowable concentrations, and this is potentially

harmful to biological life.

In 2014, chao su, et al have refered to the excessive deposition of toxic heavy metal like
mercury, chromium, lead, into the soil by human activities.

In 2002, Naim sezgin, H.Kurtulus Ozcan et al reported on Heavy metals in the street dust
pollution which release high emissions of Ni, Cu, Zn, and Pb.

In 2004, Tong –Bin Chen, et al to assess the concentration of toxic heavy metals in the Urban
park.
MATERIALS AND METHODOLOGY
SOIL SAMPLING:

In the present study the soil samples were collected from different industrial based areas of
Visakhapatnam. Each soil sample was obtained at the depth of 15 to 30 cm. After collecting the
samples were immediately placed in a fresh plastic bag and sealed tightly and are transported to
laboratory.

ANALYSIS OF CHROMIUM (CR) AND NICKEL (NI):

The soil is spreaded on a clean sheet placed on flat surface and air dried for 24 hours. The dried
soil was sieved on a 2mm sieve. From the sieved soil 5 grams of soil was taken and put in a
beaker. 10 ml of nitric acid / perchloric acid, ratio 2:1 was added and the sample was digested.
Next HCL and distilled water is added to the digested at the ratio of 1:1 and the mixture was
digested again for 30 min. After complete digestion, the sample was allowed to cool at room
temperature. The digested sample was taken into the volumetric flask and was made up to the
mark with distilled water. Determination of the metal was done by spectrophotometer at their
wavelengths.[B.A.adelekan and k.D.abegunde 2011]

PARAMETERS:

PH:

APPARATUS REQUIRED: pH meter

REAGENTS: Distilled water, standard buffer solution

PROCEDURE: The sample suspension is made by taking the sample and distilled water in the
ratio of 1:5. It was stirred for ½ hour and the pH of the suspension was noted using a pH
meter .The pH meter initially standardized with 4.0, 7.0 and 9.2 buffer solution.

ELECTRICAL CONDUCTIVITY:
APPARATUS: Conductivity meter, thermometer, glassware to prepare soil suspension, balance,
sieve, glass rod and beaker.
REAGENT: Distilled water, 0.1N KCL

PROCEDURE: The conductivity meter is first calibrated standard 0.1N KCL .A soil suspension
of 1:5 is prepared by dissolving 5gms of well –sieved soil distilled water. The sample was taken
in a beaker and the conductivity bridge is dipped into the sample and measured EC in milli
Mhos/cm.

ORGANIC CARBON:

It was estimated Walkley & Black‘s rapid titration method.

REAGENTS:

(1). 1N potassium Dichromate dissolved 49.04g of K2cr2O7 in distilled and diluted to 11.

(2).1N FAS: dissolve 39.3g of FAS in 50 ml distilled water .To this add 10 ml H2SO4 and dilute
it to 100 ml distilled water.

(3).DPA indicator: Dissolve 0.5 gms of DPA in a mixture of 20ml distilled water and 100ml
conc. H2SO4.

(4).Conc. H2SO4.

(5).H3PO4.

PROCEDURE:

0.5 gms of sample was taken in a conical flask. To it 10ml of K2CR2O7 and 20ml
of conc. H2SO4 were added. The components were mixed by gentle swirling. After allowing to
stand for ½ hour, the solution was diluted with 200ml DW. To the above solution, 10ml of
H3PO4 and 1ml of DPA were added. Then the solution was titrated against 1NFAS till blue
colour changes to brilliant green.

CALCULATION:

% organic carbon = [(V1-V2)/W*0.03*100

Where

V1= vol of K2CR2O7.

V2= vol of FAS used.

W= weight of sample (in gms).

ESTIMATION OF CHROMIUM:

REAGENTS:

 Stock chromium solution.

 Standard chromium solution.

 1:1 Sulfuric acid.

 Ortho –phosphoric acid (H3PO4).

 Di-phenol carbozide sol (DPC).

Procedure:

 Standard solution ranging from 1ml to 10ml is taken in 100ml volumetric flask.
 To this 2 ml of 1:1 H2SO4 solution is added and 2 drops of H3PO4 is added.

 2ml of DPC is also added and is made upto 100ml with distilled water by using
100ml volumetric flask.

 Let it stand for 10 minutes for full colour development

 The absorbance is measured at 540nm.

Estimation of Nickel:
Reagents:

 Nickel stock solution

 Standard nickel solution.
  Sodium citrate.
 Iodine solution.
 0.5N HCl.
 0.5N Dimethyl Glyoxine.
PROCEDURE:

 Standard solutions ranging from 1ml to 10ml are taken in 50ml volumetric flask.

 To this 20ml of 0.5N(HCL) solution ,10ml of sodium citrate solution 2ml of Iodine
solution,4ml of Dimethyl Glyoxine solution are added &made up to 50ml flask with
distilled water.

Let it stand for 10mintues for full colour development. The absorbance of the blood colour
complex is noted as 445nm.
RESULT AND DISCUSSION
PH:

Soil pH is considered as master variable as it controls physical, chemical, biological properties of

soil. It influences the availability of essential nutrients. Soil ph also depends on other properties
like buffering capacity, organic carbon and clay. [Kshudiram Chakrabordy et al2015].The PH in
soil samples from industrial areas was found to be 7.01 to 8.23.

ELECTRIC CONDUCTIVITY:

The electric conductivity of soil varies depending on the amount of moisture held by soil
particles (W.L.O jmon and Mohammed 2014). When electric conductivity increases it may lead
to soil toxicity.

Electric conductivity in soil collected from different areas was found to be 0.04 to 0.71mmhos.

The solubility of heavy – metal ions in soil was mainly influenced by Electric conductivity.
(Jayashree Deka and H.P sarma 2001). Soil electric conductivity can serve as a proxy for soil
properties such as organic matter and cation exchange capacity.

ORGANIC MATTER:
Organic matter influences many of the physical, chemical and biological properties and is
influenced by soil structure, soil compressibility and shear strength. In addition, it also effects
the water holding capacity, nutrient contribution, biological activity, water and air infiltration
rates [suryakanta2015].Among the various reactive soil organic matter has large sorption
capacity towards metals [Yin et al,2002].In soil metal and soil organic matter interaction has
various consequences both on solubility, mobility and bioavailability of metals [Boucher et al
2005]. The organic matter in soil from industrial area was found to be 22.54%to34 .96 %.

CHROMIUM:
Chromium (Cr) values in soil vary according to the area and degree of combination from various
anthropogenic agents. The mobilization of heavy metals into the biosphere by human activities
has become an important process in geo-chemical cycling of these metals. (TONG-BING-
CHEN,YUAN-MING-ZHEN 2005).Heavy metals in soil can also generate Air-Borne particles
in dust which may effect environment quality(CYRYS.et 2003,GRAY.et 2003).The soils around
the study area have chromium concentration ranging from 0.8 to 3mg/kg . The optimum levels
of chromium which can be present in the soil 1to 300010(mg/kg).

NICKEL:
The soil concentration of nickel is mainly attributable to the parent material of soil .It has been
proved that nickel is essential for the considerable growth of many species (vertebrates), plants
and micro organisms .It may even be beneficial at lower levels. [Crystos –Dsadilas et al 2008].
The poisonous effects of nickel results from its ability to replace other metal ions in enzymes,
proteins and cellular compounds. The uptake of nickel into plants is modulated by the ph of soil.
[Pawel harasim, Tadeusz Filiek 2015].With decreasing Ph ,the solubility and mobility of nickel
increases so soil ph is the major factor controlling nickel. [Yhaya Ahmed lyak 2011]. We have
estimated nickel in soil from industrial area was found to be 5to17.4 mg/kg.
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