CHAPTER 1

Impact of chemical industries on aqueous environment

 1 Chapter 1

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. Man’s

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

 2 Chapter 1

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 earth’s water is in oceans. Only 3.0% of

the world’s water is non-saline fresh water. 75% of the earth’s 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 earth’s crust.

 3 Chapter 1

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

 4 Chapter 1

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.

 5 Chapter 1

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

 6 Chapter 1

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.

 7 Chapter 1

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.

 8 Chapter 1

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.

 9 Chapter 1

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 naphthalene–formaldehyde 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 [36–41].

 10 Chapter 1

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

 11 Chapter 1

μgl-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<-1) and strongly

hydrophilic in nature. Most of the aromatic sulfonic acids with a

hydrophobic alkyl chain are biodegradable compounds. Aromatic sulfonic

acids substituted with nitro, hydroxy and amino groups are more difficult

to degrade. Despite the widespread use of aromatic sulfonic acids, very

little is known about their toxicology, ecotoxicology and environmental

behavior [34]. Because of their low octanol–water partition coefficients (log

Kow < 2.2) [34,35], they possess high mobility within the aquatic system.

Therefore, they can easily cause pollution of surface waters, as they are
 12 Chapter 1

regularly found in natural waters [7,8,11,13,18,19,23–28]. The

concentrations encountered in wastewaters from chemical industries and

water treatment plants are much higher, values in the mgl-1 range have

been reported [22,27,36–39]. 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.

 13 Chapter 1

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

 14 Chapter 1

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].

 15 Chapter 1

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.

 16 Chapter 1

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 SO3Na SO3H SO3H SO3H

NO2 NO2 NH2 NHCOCH3
NH2
NaHSO3 Fe + HCl (CH3CO)2O
+
acetylation

NO2 NO2 NH2 NHCOCH3 NHCOCH3

MPDSA AASA

Fig: 1.3 Manufacturing processes of MPDSA and AASA.

 17 Chapter 1

Fig: 1.4 3 Manufacturing processes of DASDSA and ANSDSA

NO2 NH2
NO2 NHCOCH3

Cl SO3Na SO3H SO3H

NaHSO3 Fe+HCl (CH3CO)2O
Acetylation

NO2
NO2
NH2 NH2
PPDSA PPDSAA
NaHS

NH2

SO3H

NO2
PNAOSA

Fig. 1.5 Manufacturing processes of PPDSA, PPDSAA and PNAOSA.

 18 Chapter 1

NH 2 SO3H NH 2

HO 3S SO3H NH 2 SO3H

NH 2 NH 2 NH 2

PPDDSA MPDSA PPDSA

NHCOCH 3 NHCOCH NH 2
3

SO3H SO3H

NH 2

SO3H NH 2 NO 2
PPDSAA PNAOSA
AASA

SO3H CH 3

NO 2 SO3H
H2N N N SO3H

NO 2 NO 2

PAABSA
DNBSA PNTSA

SO3H HO 3S SO3H HO 3S

H H
O2N C C NO 2 O2N C C NH 2
H H

DNSDSA ANSDSA

SO3H HO 3S SO3H HO 3S

H H
H2N C C NH 2 N3 C C N3
H H

DASDSA BASDSA

Fig. 1.6 Chemical structures of benzene and stilbenesulfonic acids studied

in the present investigation.

 19 Chapter 1

Table: 1.2 Chemical structures and abbreviations of benzene sulphonates

studied in the present investigations

R1

R6
R2

R3

R4

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)
 20 Chapter 1

Table 1.3 Chemical structures of stilbenesulfonic acids studied in the

present investigation

R3
R1

R2 HC CH R4

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)
 21 Chapter 1

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
 22 Chapter 1

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 24 Chapter 1

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