CHAPTER 1 Impact of chemical industries on aqueous...
Transcript of CHAPTER 1 Impact of chemical industries on aqueous...
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CHAPTER 1
Impact of chemical industries on aqueous environment
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1.1 Introduction
Humans have always inhabited two worlds. One is the natural world of
plants, animals, soils and water. The other is of social institutions and
artifacts that we created for ourselves using science and technology. Mans
quest for progress is always eternal. In his zeal to achieve scientific and
technological advancement, man is unwittingly endangering many of the
life-supporting systems on which we depend. To ensure a sustainable
future and the balance of the ecosystem as a whole for ourselves and
future generation, we need to take suitable measures to protect and
manage environment.
Once upon a time, the basic amenities for living organisms air, land
and water were pure, virgin, uncontaminated and basically most
hospitable for living organisms. But today the situation is reversed. Due to
scientific and technological advancement we are subjected to the horrible
ecological crisis that is, pollution of environment. Pollution is an
undesirable change in the physical, chemical and biological
characteristics of air, water and land that effect human life, industrial
progress, living conditions and cultural assets.
1.2 Aquatic environment
Water is one of the most important assets of nature, which is vital
for life. Without water the present life forms could not exist. It is an
essential natural resource for ecological sustenance, agricultural
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productivity, environmental purity, industrial growth, power production
and enrichment of land and air. Its protection and management is
fundamental to the survival of our civilization.
More than the 97% of the earths water is in oceans. Only 3.0% of
the worlds water is non-saline fresh water. 75% of the earths surface is
covered with water. However, 79% of all fresh water is bound up in
glaciers and ice caps. Only 1% of freshwater is found in lakes, rivers and
soils and 20% is present as ground water. The distribution of water on
earth crust is shown in Figure 1.1. The explosive growth in population has
put an increasing strain on water resources. Finding adequate supplies of
freshwater to meet our ever-increasing needs, and maintaining its quality
is a problem of the day.
The shortage of natural resource of healthy water appears common in
poor, over populated countries, which cannot afford to install and operate
expensive water treatment facilities. Approximately 15 million children die
from water borne diseases before reaching the age of five. Therefore, there
is still a real need for new, more economic methods of water purification.
Fig. 1.1 Distribution of water on earths crust.
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Water plays an important role in meeting the ever-increasing
demands for various domestic, agricultural and industrial uses. Alarming
growth rates of population, industry and agricultural practice have not
only increased the exploitation of water but have also contributed towards
the deterioration of its quality. Therefore, the preservation and
improvement of water quality is of great importance for human well being
as well as for the sustainability of clean environment. Any chemical,
physical or biological change in the quality of water has a harmful effect
on any living being that drinks and uses it. When humans drink polluted
water it often has serious effects on their health. Water can be polluted by
a number of inorganic and organic compounds such as oil, plastics and
pesticides, which are harmful to humans and all plants and animals.
1.3 Industrial development and its impact on environment
The phenomenally rapid development of technology has enormously
increased our ability to produce goods and enhanced the standard of
living. However, it has generated a secondary phenomenon viz., the
environmental pollution. This has had the contrary effect of leading to
deterioration in the quality of life. For much of history, an enhancement in
the quality of life arising from new technology has overshadowed its
negative effects upon the environment. Recently, however, there have been
some doubts as to whether further development of technology will
necessarily guarantee an improvement in the quality of life. It is seen that
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an increase in productivity accelerates not only the exhaustion of raw
materials, but also the deterioration of the environment through the
discharge of wastes. On one side environment is a source of energy and
materials, which are transformed into goods and services to meet human
needs; on the other hand, it is a sink for the wastes and emissions
generated by producers and consumers.
The number and variety of chemical products used in every day life
is growing rapidly. For their manufacture, new chemicals are sometimes
used which have unknown or detrimental health effects. These chemicals,
no doubt have brought immense benefit to society, but they have also
brought potential dangers, largely through the waste generated during
their production. Tens of millions of tons of toxic or otherwise hazardous
substances enter the environment every year. One of the most worrying
features of the problem is that very little is known about the long-term
consequences of exposure to the chemicals. We know now that over longer
periods some of these can cause cancer, delayed nervous damage,
malformations in urban children, and mutagenic changes. Many other
chemicals are likely to have similar effects, but since these take time to
show and their causes are hard to pinpoint, we do not yet know which are
the dangerous ones. The situation is even more problematic because, once
they are in the environment, these chemicals disperse and spread in a
very complex manner and may be get converted into other substances
which have varied effects.
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A typical example of a threat to the environment emanating from
chemicals could be seen from the history of the use of pesticides. The
introduction of a new pesticide into the market is determined after a
research of 2-3 years if it does not show a detrimental effect on human
health. After such a short research period it is hard to determine
unequivocally whether or not a chemical has mutagenic and/or
carcinogenic properties. Very often the grounds on which a decision to use
a chemical is made are subjective and controversial.
The development of technology, for all its consequences, has
improved the quality of life by making our existence richer and more
meaningful. In this sense technology has not been an antagonist to the
environment. However, some doubt arises as to whether this will remain
so. We are at a stage where it is not clear whether further development of
technology will really improve our quality of life or cause it to deteriorate
by rendering the environment less healthy. It is now known that pollution
in some parts of the world has reached a level close to an ecological
catastrophe.
1.4 Chemical industry
Indian Chemical Industry is one of the largest and most advanced
among the ones in the developing countries. Indian Chemical Industry
produce include petroleum products, polymers, fertilizers, dyes and dye
intermediates, drugs and pharmaceuticals, pesticides, edible and
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industrials oils, synthetic paints, inks and numerous specialty organic
and inorganic chemicals [1-5]. Major portion of the Indian Chemical
Industry includes textile and pharmaceuticals industry.
1.5 Contamination of water resources
Water pollution is generally due to rapid industrialization without
proper arrangements for treatment and disposal of waste products. Many
industries discharge their untreated waste in the immediate neighborhood
or in some nearby low lying areas mostly in open channels which join
various surface water bodies such as large ponds, streams, rivers etc. The
pollutants of these waste materials after affecting soils and surface water
seep down to the ground water system along the entire course of fluid
flow. In hard rock areas fractures, fissures and joints provide additional
pathways for a fast movement of pollutants into ground water systems.
Recently, a new problem has arisen in well-developed countries.
Because of the concentration of population in big cities and intensive
industrial activities, man-made chemicals have more and more
contaminate natural water reservoirs. The presence of these in waterways
leads to the disturbance of natural self-purification processes. Water from
polluted reservoirs can become unsuitable for drinking purposes. The
most serious problem is caused by non-biodegradable chemicals, which
tend to accumulate in the bodies of living creatures. The most dangerous
of these chemicals are heavy metals and chlorinated organic compounds.
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The need for their removal could result in a continuous increase in the
cost of providing safe drinking water. Elimination of the negative impact of
these pollutants on human health is one of the important tasks of today.
1.5.1 Sources of pollution
Principal sources of water pollution are:
industrial discharge of dyes and intermediates
industrial discharge of pharmaceuticals
industrial discharge of chemical wastes and byproducts
discharge of poorly-treated or untreated sewage
surface runoff containing pharmaceuticals
surface runoff containing pesticides and herbicides
surface runoff containing spilled petroleum products
surface runoff from construction sites, farms, or paved and other
impervious surfaces e.g. silt
discharge of contaminated and/or heated water used for industrial
processes
acid rain caused by industrial discharge of sulfur dioxide (by
burning high-sulfur fossil fuels)
excess nutrients added by runoff containing detergents or fertilizers
underground storage tank leakage, leading to soil contamination,
hence aquifer contamination.
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1.6 Organic pollutants in water
The presence of organic substances in water is a matter of
increasing concern to the water industry, environmentalists and the
general public in view of the possible health hazards likely to arise to both
human and animal life represented by domesticated and wild animals,
bird and fish. Awareness towards this hinges on three facts:
i) The increasing interest of public in environmental matters,
ii) An increased usage of organic materials in commerce coupled
with the much wider variety of organic substances used
nowadays,
iii) The availability of analytical methods sensitive enough to
determine very low concentrations of these substances, the
presence of which, people were normally unaware till the recent
past.
It has been estimated that river waters contain up to two thousand
different organic substances over a wide concentration range, many of
which survive processing in the water works and occur in potable water
with possible health implications (Fig.1.2). The Food and Drug
Administration in United States of America, is systematically working its
way through screening tests on the substances so far identified in water,
but this is a process that will take many years to complete.
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Fig. 1.2 Different ways of water pollution 1.7 Aromatic sulfonic acids
Aromatic sulfonic acids like benzene-, naphthalene-, anthraquinone
and stilbene-sulfonic acids are large-volume chemicals widely used in
industrial and domestic processes. For example, substituted benzene and
naphthalenesulfonic acids are used in the chemical industry as
intermediates for the manufacturing of pharmaceuticals, dyes and tanning
agents. Sulfonated naphthaleneformaldehyde condensates are important
commercial plasticizers for concrete, dispersants and tanning agents [7
11]. Sulfonated azo dyes are extensively applied in the textile industry to
color natural fibers, inks and pigments [12]. In the paper industry
stilbenesulfonic acids are applied as whiteners [13,14]. Alkanesulfonic
acids and linear alkylbenzenesulfonic acids (LASs) are frequently used
anionic surfactants in detergents and laundry [3641].
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Due to high persistency in environmental biological systems, these
compounds accumulate in natural ground and surface waters and
industrial effluents [7,8,11,18-29] as consequence of industrial activity or
leaching processes occur in landfills [21]. The biodegradation mechanisms
of aromatic sulfonic acids have been reviewed by Cook et al. [31].
Unsubstituted aromatic sulfonic acids and aromatic sulfonic acids with an
additional methyl group are readily degradable, while aromatic sulfonic
acids substituted with nitro, hydroxy and amino additional groups are
more difficult to degrade. As a consequence, these compounds are
reported to resist biodegradation in activated sludge processes for sewage
treatment [31]. Castilo et al [6] have identified 3-nitrobenzenesulfonic acid,
4-chlorobenzenesulfonic acid, 1-amino-6-naphthalenesulfonic acid, 1-
hydroxy-4-naphthalene sulfonic acid, 1-amino-7-naphthalenesulfonic acid
and 2-naphthalenesulfonic acid in tannery and textile wastewasters.
Alanso et al [18,22] and Loos et al [32,33] have identified the benzene and
naphthalenesulfonic acids in treated and untreated wastewaters of
industrial wastewater treatment plants in Sweden and Spain. 3-
Nitrobenzenesulfonic acid 4-methylbenzenesulfonic acid and 2-
naphthalenesulfonic acid were found even in the treated effluents of
wastewater treatment plants. Loos et al [19] and Storm et al [23] have
identified the naphthalenesulfonic acids in the municipal wastewater
treatment, dying bath and textile wastewaters in Germany. Kok et al [28]
have identified the naphthalenesulfonic acids in river Elbe, Germany in
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gl-1 level. Redin et al [1] have detected the 5,5'-methylenebis-2-
naphthalenesulfonic acid, 5,8'-methylenebis-2-naphthalenesulfonic acid
and 8,8'- methylenebis-2-naphthalenesulfonic acid in rivers Schussen and
Rhine, Germany. These observations indicate that the aromatic sulfonic
acids are not completely degraded in the wastewater treatment plants and
released into the water bodies. Although the aromatic sulfonic acids have
low acute toxicity and show no genotoxic or carcinogenic effects [34], their
persistence constitutes a potential ecotoxicological risk and a problem for
drinking water supplies [27]. Recently, there is an upsurge of interest in
the analysis and treatment of these compounds in aqueous environment
due to their possible photo as well as bio chemical degradation leading to
the formation of toxic species.
1.7.1 Effect of aromatic sulfonic acids on environment
Aromatic sulfonic acids are very acidic (pKa
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regularly found in natural waters [7,8,11,13,18,19,2328]. The
concentrations encountered in wastewaters from chemical industries and
water treatment plants are much higher, values in the mgl-1 range have
been reported [22,27,3639]. Knowledge about the presence and
concentration of such compounds in the environmental compartments is
therefore of great importance for the protection of our natural waters.
Hence effective analytical methods are to be constantly devised for
identifying these compounds in the aqueous environment.
1.8 Statement of the problem
The growing pace of industrialization in our times has certainly changed
the face of modern day urban India not only in terms of providing better
opportunities of livelihood but also adding manifold to the comforts of life
of an average human being. However, while its advantages are enormous,
its disadvantages too cannot be underscored. It has also brought in its
wake the problem of the contamination of environment air, soil, surface
water bodies and ground water, aquifer as well the complex problems of
waste disposal. These have resulted in imperiling the lives of not only
human beings but also livestock and the flora and the fauna in the
absence of judicious and insightful planning in the situating of industrial
units, adequate development of infrastructure and suitable waste
management facility. These problems have multiplied increasing the
health and environmental hazards.
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Industries providing inorganic chemicals, fertilizers, dyes, paints,
pharmaceuticals and batteries were identified as hazardous as their waste
is considered to be non-degradable and normally tedious to recycle. There
is a view that 70% of the available surface water in India is polluted. The
major sources of this water pollution are: discharge of domestic sewage as
well as industrial effluents that contain organic pollutants, chemicals,
heavy metals and other wastes from agricultural and mining activities.
Most of the rivers and water bodies have become channels of poison:
especially big rivers, which were earlier, considered as lifelines have
undergone a metamorphic change and now have become agents of
death.
The city of Hyderabad as the capital of Andhra Pradesh has recently
emerged as the hub of economic, industrial and informat ion technology
revolution. As a result it has undergone unprecedented and large-scale
change in the last two decades. Industrialization has brought with it an
urban explosion. Presently the metropolitan area of Hyderabad: Ranga
Reddy and Medak districts together are one of the fastest growing
industrial areas in the entire country. Long term plans of development
haphazardly conceived without judicious planning have resulted in
making several compromises in the use of soil and surface and ground
water in the region. It has been found that in certain areas like
Patencheru, Jeedimetla and Balanagar industrial areas in and around
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Hyderabad region, there is hardly any dependable source of safe portable
water [40].
Usually the establishment of polluting industries is restricted within
15Km of a fresh water bodies. This has not been adhered to in several
cases in and around Hyderabad. It may be sighted here that in case of
Patencheru Gaddapothram Bolaram industrial area, river Nakkavagu
which is the main tributary of river Manjira and drains that area is located
within 5 km from Patencheru IDA and the slope is < 1 %, the sediment
load and the contaminant flow poses serious hazard to Manjira water
supply system. Katechan IDA located towards the south of Hyderabad in
another contaminated area. The Balanagar - Jeedimetla Kukatpally IDA
which drains into Hussain Sagar is highly polluted and poses a very
serious health hazard to the people in the residential colonies at the lower
end. There are around 160 such industrial units producing hazardous
substances in Ranga Reddy district, Medak and Hyderabad region. Table
1.1 indicates the categories of industries in Hyderabad and its
surroundings. The unabated air and water pollution has made Patancheru
a hell on earth as coined by Prof.John E Bonine of USA. He said that
industrialization brought to Patancheru not human progress but the very
antithesis of development. Neither the management of industry nor the
bureaucracy thought of the disposal system for wastes and this ignorance
or negligence of theirs brought misery to the people of this area [41].
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In view of such a high degree of water pollution in and around
Hyderabad it is proposed to study the levels of aromatic sulfonic acids in
industrial effluents. Further it is proposed to develop efficient treatment
procedures viz., biodegradation and an advanced oxidation processes for
degradation of benzenesulfonic acids in aqueous environment.
General 3 Manufacturing processes of MPDSA, AASA, DASDSA, ANSDSA
PPDSA, PPDSAA and PNAOSA are shown in Figs. 1.3, 1.4 and 1.5
respectively.
Table 1.1 Types of industries in Hyderabad region.
Type of industrial Hyderabad district RR district Medak district
unit
Pharmaceuticals 18 47 03
Petrochemicals 2 0 0
Paint & varnishes 03 01 01
Dyes & intermediates 06 03 02
Chemical & fertilizers 26 48 04
1.9 Aims and objectives
1. Development of high performance liquid chromatographic profiles
for separation and determination of 13 aromatic sulfonic acids viz.,
benzene and stilbenesulfonic acids (Table 1.4).
2. Development of electrospray ionization-mass spectral profiles (ESI-
MS) and LC-ESI-MS profiles of the selected pollutants in order to
detect and determine them in aqueous environment.
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3. Application of developed HPLC and ESI-MS profiles for detection
and determination of aromatic sulfonic acids in industrial effluents.
4. Optimization of advanced oxidation processes viz., TiO2/UV and
Fe2+/H2O2/UV processes for degradation of benzenenesulfonic acids
viz., metaphenylediaminesulfonic acid (MPDSA), 3-aminoacetanilide-
4-sulfonic acid (AASA), paranitrotoluenesulfonic acid (PNTSA) and
2,4-dinitrobenzenesulfonic acid (DNBSA) in aqueous environment.
5. Isolation of microorganisms Arthrobactor species from industrial
effluent and study on their use in the biodegradation of
benzenesulfonic acids viz., metaphenylediaminesulfonic acid
(MPDSA), 3-aminoacetanilide-4-sulfonic acid (AASA),
paranitrotoluenesulfonic acid (PNTSA) and 2,4-
dinitrobenzenesulfonic acid (DNBSA) in aqueous environment.
Cl
NO2
NO2
SO3Na
NO2
NO2
SO3H
NH2
NH2
SO3H
NHCOCH3
NHCOCH3
+NaHSO3 Fe + HCl (CH3CO)2O
acetylation
SO3H
NH2
NHCOCH3 MPDSA AASA
Fig: 1.3 Manufacturing processes of MPDSA and AASA.
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Fig: 1.4 3 Manufacturing processes of DASDSA and ANSDSA
NO2
Cl
NO2
NO2
SO3Na
NO2
NaHSO3 Fe+HCl
NH2
NH2
SO3H
Acetylation
(CH3CO)2O
NHCOCH3
SO3H
NH2
NH2
SO3H
NO2
PPDSA PPDSAA
PNAOSA
NaHS
Fig. 1.5 Manufacturing processes of PPDSA, PPDSAA and PNAOSA.
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NH2
NH2
HO3S SO3H
NH2
NH2
NH2
SO3H
NHCOCH 3 NHCOCH 3
NH2
SO3H
NH2
NO2
SO3H
SO3H
NO2
NO2
NO2
SO3H
SO3H
NH2
NH2
SO3H
CH3
H2N SO3HN N
O2N NO2
HO3SSO3H
O2N CH
HC
HO3SSO3H
NH2
CH
HC
HO3SSO3H
H2N NH2 N3 N3CH
HC
HO3SSO3H
PPDDSA MPDSA PPDSA
AASA PPDSAA PNAOSA
DNBSA PNTSAPAABSA
DNSDSA ANSDSA
DASDSA BASDSA
CH
HC
Fig. 1.6 Chemical structures of benzene and stilbenesulfonic acids studied
in the present investigation.
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Table: 1.2 Chemical structures and abbreviations of benzene sulphonates
studied in the present investigations
R1
R3
R4
R6R2
Compound R1 R2 R3 R4 R6
Paraphenylene diamine-2,6-disulfonic acid NH2 SO3H H NH2 HO3S
[PPDDSA]
Metaphenylene diamine-4-sulfonic acid SO3H NH2 H NH2 H
[MPDSA]
2-Amino-4-acetanilidobenzenesulfonicacid NHCOCH3 H NH2 HO3S H
(AASA))
Paraphenylene diamine-2-sulfonic acid NH2 SO3H H NH2 H
[PPDSA)
Paraphenylene diamine-2-sulfonic acid- NHCOCH3 SO3H H NH2 H
acetyl (PPDSAA]
Paranitroaniline ortho sulfonic acid NH2 SO3H H NO2 H
(PNAOSA]
2,4-Dinitrobenzene sulfonic acid SO3H NO2 H NO2 H [DNBSA]
Paranitrotoluene sulfonic acid CH3 SO3H H NO2 H
[PNTSA)
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Table 1.3 Chemical structures of stilbenesulfonic acids studied in the
present investigation
HC CH
R3R1
R4R2
Compound R1 R2 R3 R4
2,4-Dinitrostilbene-2, 2-di sulfonic acid SO3H NO2 SO3H NO2
(DNSDSA)
4-Amino-4'-nitro stilbene-2, 2-disulfonic acid SO3H NH2 SO3H NO2
(ANSDSA)
4,4'-Diaminostilbene-2, 2-disulfonic acid SO3H NH2 SO3H NH2
(DASDSA)
Bis azidostilbene disulfonic acid SO3H N3 SO3H N3
(BASDSA)
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Table1.4 Common name, Abbreviation, IUPAC name and CAS registry
number of the studied aromatic sulfonic acids
Compound Abbreviation IUPAC name CAS No.
Paraphenylenediamine- PPDSA 2,5-diaminobenzene 88-45-9
2-sulfonic acid sulfonic acid
Metaphenylenediamine- MPDSA 2,4-diaminobenzene 3177-22-8
4-sulfonic acid sulfonic acid
4-Aminoacetanilide-2- 2-AASA 2-acetamido-5-amino 6973-05-3
sulfonic acid benzenesulfonic acid
3-Aminoacetanilide-4- 3-AASA 4-acetamido-2-amino 88-64-2
sulfonic acid benzenesulfonic acid
Paranitroaniline- PNAOSA 2-amino-5-nitro 96-75-3
orthosulfonic acid benzenesulfonic acid
Paranitrotoluene PNTSA 2-methyl-5-nitro 121-03-9
sulfonic acid benzenesulfonic acid
2,4-dinitrobenzene DNBSA 2,4-dinitrobenzene 886-62-1
Sulfonic acid sulfonic acid
Paraaminoazobenzene PAABSA 4-aminoazobenzene- 104-23-4
sulfonic acid 4'- sulfonic acid
4,4'-diaminostilbene- DASDA 2,2'-(1,2-ethenediyl) 81-11-8
2,2'-disulfonic acid bis (5-amino) benzene-
sulfonic acid
4-amino-4'-nitro-
stilbene- ANSDA 5-amino-2-[2-(4-nitro- 119-72-2
2,2'-disulfonic acid 2-sulfophenyl)ethenyl]
benzenesulfonic acid
4,4'-dinitrostilbene DNSDA 2,2'-(1,2-ethenediyl) 128-42-7
2,2'-disulfonic acid bis (5-nitro)benzene-
sulfonic acid
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