Acknowledgements
I thank Mr. E. Deenadayalan, General Secretary, The Other Media, for pursuing the funding agency to release funds for the project. Mr. Deena has been very much involved in every step of the progress of the project, making it sure that I am able to do the work without any problem. Mr. Deena has spared his invaluable time to discuss with me at every stage of my work. I am very much indebted to him.
I express my deep sense of gratitude to Ms. Taranjit Birdi, Coordinator for the Fact Finding Mission for Bhopal’s Gas Tragedy for considering me as one of the members for the mission. Ms. Birdi, has given me constant support, encouragement and has given her precious time in discussing the progress of the work, at every stage of the project. I owe a lot to Ms. Birdi as she helped me all through the project.
I thank, Mr. Satinath Sarangi, Chairman, Sambhavana Clinic, for providing assistance at a very crucial juncture, where everything seemed hopeless and a point where the work could have been shelved, if not for his timely assistance. Mr. Satinath, metallurgical scientist himself, anticipated my problems and thereby did the needful. I thank very much two of his colleagues, Mr. Diwakar. K. Sinha and Mr. Ramesh
Mishra for collecting breast milk samples from the field and storing them in the best possible way, until analyses.
I am grateful to Mr. Ravi Agarwal, Coordinator, Srishti, for chanelising the funds for the project and providing his staff to take care of the accounts of this project.
My sincere thanks to two esteemed chemical scientists – Dr. Padma Vankar & Dr.
Rashmi Sanghi, Indian Institute of Technology, Kanpur (IIT-K), for carrying out a very tedious analysis with a lot of dedication.
I thank a few of my friends - Mr. Nityanand Jayaraman, formerly with Greenpeace,
Ms. Leena, The Hazard Centre, Ms. Sunita Dubey, Toxic Link and Mr. Soe, The
Other Media., for their help. I thank Mr.R.S. Sharma from the Toxic Link for his help.
I express my gratitude to Hivos, for providing funds to pursue the project.
I am indebted to my parents for giving me support at every moment in life.
Last, but not the least, my dear wife, Jaya, who encouraged me all through the work, helped me collect samples from the field, translated and computed mathematical values derived from the analyses into self explanatory graphs and most of all kept my morale high, all through the project.
Contents
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Acknowledgements
Introduction
Union Carbide India Limited
Manufacture of Sevin
MIC storage
Factory- 2 nd December1984
The Disaster
Safety system in the factory
UCIL’s financial status before disaster
Compensation
Post-disaster era
ICMR’s 5.5 crore rupees projects
Fact Finding Mission of Bhopal Gas Disaster
Survey of Environmental and Human Contamination
Materials & Methods and Results for Heavy metals
Materials & Methods and Results for Organic Compounds 30
Graphical Representation:
Heavy Metals
Volatile Organic Compounds
Pesticides
Halo-organics
Discussion
Toxicology of compounds
Overall Contamination
References
2
by
Introduction:
3
The world’s biggest chemical disaster has been the 1984 Bhopal Gas Tragedy, which is responsible for claiming over five thousand of lives and rendering more than two lakh people morbid. The crucial question of how a calamity of such a magnitude had been allowed to occur? Unless, safety norms, preventive maintenance and management failures had been flouted altogether, the mishap would have never occurred.
What exactly poisoned so many lives is still a matter of conjecture. The plant was undoubtedly manufacturing carbaryl (Sevin), a formulation of it with lindane (gamma HCH), small quantities of aldicarb (Temic) and butaphenyl methyl carbamate, all destined for use in the Indian market. However, there has been confusion surrounding the nature of the poisonous gas that took so many lives. Was the gas MIC or phosgene, or a mixture of both or some other deadly toxic gas? The examination of the residues from the faulty tank, revealed twelve compounds. These were MIC, its timer called MICT,
Dimethyl urea, Trimethylurea, Trimethylbiuret, Dimethyl isocyanurate, Cyclicdione, Monomethyl amine, Dimethylamine and Trimethyl amine, HCN and Nickel salts. Interestingly, the parent carbide factory is still tight lipped about the nature of the gas. If they had indicated the nature of the gas or the antidote, immediately after its release, perhaps, thousands of lives would have been saved, but the company would have to open its Pandora box. Beyond any doubt and taking in view of the magnitude of the disaster, these gases were perfect chemical warfare agents. It is quite possible that deadly gases or its initial cocktails were being manufactured in India, and were being shipped elsewhere, either to the parent company or to other points where they could be put in shells or missile systems and used in chemical warfare.
The developing countries would be the right choice since labor is extremely cheap, compensation are just for namesake where the cost of human life is negligible when compared to the developed country.
Hence the cost-benefit ratio is in favour of
Developing countries. Why has it become so important to doubt the companies’ antecedents?
The UCIL had a large stockpile of phosgene when the disaster had occurred. The quantity of the phosgene stockpiled were many folds more than what was required for the manufacture of the pesticide carbaryl. Phosgene, chemically known as carbonyl chloride is a deadly gaseous toxin, used in World war-II, as a lethal chemical warfare agent. The MIC release has shown the world its potential to annihilate mankind and its use as a good chemical warfare agent.
What happened on the night of 2nd December 1984?
Union Carbide India Limited.
The parent Union Carbide Corporation (UCC), West Virginia, USA, proposed the design for the plant at Bhopal, India. The parent plant had followed double standards, as it gave priority to cost considerations rather than human safety at Bhopal while at its Virginia plant human and environmental safety were priority.
The UCIL manufactured the pesticide carabaryl (Sevin), (Union Carbide, Oct, 1978).
. The production was intended primarily for demand within the country. However, the plant had a production capacity far greater than the production planned for UCIL, Bhopal. Interestingly, the demand and use in agriculture for carbaryl in India were far below the output from the UCIL plant.
4
Therefore, the UCIL plant had been running steadily under-capacity and high cost of maintenance was already being built-in (DSF-Report, 1985).
In the manufacture of Sevin, two lethal compounds available- Methyl Isocyanate (MIC) and Carbonyl
Chloride (Phosgene) are required. Initially, MIC was imported to manufacture Sevin, but in 1977, the
UCIL plant obtained the technology for the production of MIC from the parent UCC, and by 1980 the
UCIL commenced the production of MIC. The basis for the gas tragedy was essentially due to the transfer of an outdated, second-hand and unsafe technology from the MIC plant, at Danbury, USA. It is understood that Canada had refused permission for the manufacture of MIC and was subsequently shipped off to Bhopal.
Incidentally, even the most developed countries with an extremely well organised disaster and crisis management groups prohibit the manufacture or storage of MIC. For instance, France does not permit the manufacture of MIC on its territory. Both, France and West Germany, allows the storage of MIC not more than 60 tonnes, even after safety measures designed of taking worst possible scenarios.
Although, an alternative technology that does not require MIC to manufacture Sevin is available, why such a process was not commercialized and why the process involving not only the use but also the synthesis of MIC, is intriguing.
Manufacture of the carbamate pesticide, Sevin (Carbaryl).
To manufacture Sevin, there is a need to initially use three ingredients.
They are: -
1. Phosgene - (COCl
2
)
2. Monomethylamine (MMA) - CH
3
-NH
2
3. Methyl Isocyanate (MIC)- CH
3
N=C=O
Phosgene also known as carbonyl chloride is manufactured by reacting chlorine with carbon monoxide.
The chlorine for this reaction is brought to the plant in a tanker while carbon monoxide was produced from petroleum coke when it was made to react with oxygen. The UCIL had a facility to produce carbon monoxide.
The monomethyl amine was also brought in by a tanker, and was allowed to react with phosgene in the presence of chloroform to produce methyl carbamoyl chloride (MCC) and hydrogen chloride gas. The process is called phosgenatation.
The methyl isocynate (MIC) is produced when Monomethylamine (MMA) is heated.
Overviews of the chemical reactions are: -
1). COCl
2
Phosgene
+ CH
3
NH
2
------------ CH
3
MMA
NHCOCl + HCl + Heat
MCC Hydrogen Chloride
In step 1, the reaction proceeded in the presence of chloroform (CHCl
3
).
2). CH
3
NHCOCl ----------------- CH
3
N=C=O +
MCC MIC
HCl
The MIC was collected and stored in stainless steel tank while the remaining HCl, Chloroform were collected recycled for use once again.
5
3). CH
3
N=C=O + alpha napthol --------------- * OCONHCH
3
Carbaryl (Sevin)
In step 3, the reaction proceeded in the presence of carbon tetrachloride (CCl
4
).
Note: The MMA and chlorine gas was brought in by tank truck from other parts of India and stored in tanks and used whenever MIC was needed to produce Sevin
Other pesticides : Although Sevin was the major pesticide; smaller amounts of other carbamate pesticides were also manufactured using MIC. These were aldicarb (Temic) and butyl phenyl methylcarbamate and a formulation of Sevin-lindane was also made at UCIL.
Could MIC production and storage be avoided in India?
Sevin is not an affordable pesticide to Indian farmers and unlike like DDT and BHC, they were not broad spectrum. So there was actually no need to manufacture Sevin for Indian farmers and putting at risk the lives of so many people by storing and all the more producing MIC in India. Furthermore, the
Government knew that there was no provision in the state or even the country to handle a disaster, and why was this issue sidelined to produce MIC.
Earlier, UCIL used to import MIC for the production of Sevin. In 1977, the company entered into a contract with the parent company to produce MIC and by 1980, UCIL began production of MIC. There was no need to produce and store MIC in India, and even the most developed countries fear to store let alone produce MIC.
In fact, there was already a process patent by Union Carbide Corporation which does not require MIC for Sevin or other carbamate manufacture. This is a two step reaction where first, the sodium-1napthoxide is made to react with phosgene and the intermediate product of this reaction enters second reaction where it reacts with methylamine to produce reacts Sevin.
Factory - UCIL on December 2, 1984
The following sequence of events began at 10:20 pm, Sunday, December 2, 1984, near the end of the second shift. In the storage tank 610, it is understood that 41 metric tonnes (91,000 pounds or 11,290 gallons) of MIC was stored. The liquid level in this tank was 70% of capacity, which is below the maximum operating level. This level results in a headspace of 2 feet and 9 inches in the eight feet diameter tank. All the valves to and from the tank were closed except for the relief valve containing the rupture disc and the safety valve. The pressure in the tank was reported to be 2 pounds per square inch (psig) at 10:20 pm at the second shift that lasts till 10:45 pm.
At 11:00 pm (third shift), the control room operator noticed that the pressure at the tank 610 was 10 psig, however, this was not thought unusual since the tank operated between 2 and 25 psig. The field operator reported MIC leak in the structure near the Vent Gas Scrubber (VGS) and process filters, but the source of MIC was not detected.
6
At about 12:15 am on 3 December, the field operator reported a MIC release in the MIC process area.
The control room operator found that tank pressure had increased to 30 psig and within moments was beyond 55 psig, which was above the top of the scale. The operator turned the switch to activate the
VGS, but the VGC was removed from an operating mode to a standby mode. The return to operating mode from the standby mode was dependent on an activation of the circulating pump.
The reason for the release of MIC was that water had accidentally entered the storage tank 610. The presence of higher amounts of chloroform and the presence of iron from the corrosion of the stainless steel 610 tank, favored a heat generating reaction (exothermic), resulting in a release of 50,000 pounds of MIC gas in the atmosphere. This was because the safety valves became unseated for 2 hours, before being reseated *once again. However, it is quite difficult to ascertain whether other toxic gases were also released since UCIL was tight-lipped about it from the onset of the disaster.
The world’s greatest industrial disaster had occurred at the Union Carbide Plant!
The Disaster.
The disaster struck in the midst of night. Almost 3000 people died and an average of 500,000 people affected. Many died in their sleep while those who managed to run out of their homes were blinded and chocked by the gas and died of suffocation in the streets. Many died after reaching hospitals since doctors were not able to identify the poisonous gas and the neither the parent company or UCIL were ready to reveal the type of gas released. The initial acute toxic effects were vomiting and burning sensations of the sensory organs like the eyes, nose and throat followed by acute respiratory failures.
Disorders. Those who were not immediately knocked down died due to pulmonary edema (collection of liquid within the lungs) and bronchio spasm (constriction of the air passage tubes). The survivors were later found to have severe abnormalities and damages in their respiratory, gastrointestinal, musculo-skeletal, reproductive and immunological systems. Most of the survivors showed neurological disorders like depression, irritability, fatigue, disturbed balances and headaches.
Today, the aftermath victims of the Bhopal gas tragedy are those in moribund state i.e. between living and dead. Many cannot even walk for a short distance due to severe dispnoea (labored breathing), many have blurred vision and even eyeglasses have not helped them from eye watering.
For the present day victims, the society has closed its doors and the government unwilling to take needful legal action against Union Carbide Company, for absolutely no fault of theirs!
The cause! How safe was the “Safety System”?
The main reason behind the disaster is the failure of the safety systems meant to monitor, store or counter and avert any possible mishaps. The safety system comprises of Relief Valve Vent Header
(RVVH), the Vent Gas Scrubber (VGS) and the Flare tower (FT) were not maintained properly and hence not satisfactorily operating. The function of the VGS was to neutralize escaping MIC with caustic solution. The motors meant for pumping caustic solution into the VGS ware not operative. The final safety measure was the Flare tower, where the neutralized gas, if VGS was unable to cope with neutralizing the whole of the escaping MIC, the remaining would be burnt off. The line connecting the
VGS to the FT was extensively corroded due to poor maintenance and was sent for repairs without incorporating a standby system (see figure-1 .
for design for MIC storage). Also, the FT was
7
inadequately designed to perform its task, as it was only capable of handling only a quarter of the gas released. The ultimate step in the event of a leak was the water curtain designed to contain any remaining gas from the FT. This was so poorly designed that it was too short to reach the top of the flare tower. A number of pressure gauges, pumps and meters were either under repair or malfunctioning. The valves, vent lines and feed lines are to be replaced every six months but they have been used over two years. It is beyond doubt that poorly maintained accessories meant in storing the
MIC, allowed the entry of certain chemicals and water in minute quantities, which initiated a runaway reaction to spill a disaster. In fact, many clues after the accident indicate the possibility of an onset of uncontrollable reactions within the MIC storage tank 610. Water was found in the vent line connecting the tank 610 and RVVH. Also, caustic soda was found in RVVH.
Although, the UC is tight lipped about the mechanical problems that occurred during the disaster, nevertheless there are several concrete indications to show that there were serious problems associated with the MIC storage tank 610 themselves. The chilling unit meant to keep MIC at low temperature was switched off for economic reasons (DSF- Report, 1985). The meters monitoring the MIC storage tank 610 were faulty. A pressure of 20 pounds per square inch was being shown as 2 pounds per square inch (psi) by the pressure gauges. Further, it appears that even the Rupture Disc (RD) was not functioning at the time of the disaster. If the RD had ruptured, the pressure gauge connected between
RD and Relief Valve (RV) should either indicate build up of pressure or otherwise read zero in its scale. Normally, if anything has to get into the storage tank, it has to pass through the Relief valve
(RV), which would open only when the pressure exceeds a permitted value inside the MIC storage tank. Even, if the RV was faulty and water and chemicals were passing through it, still would have to pass through the RD, which is a gas tight seal, designed to rupture only when the pressure builds up beyond a threshold limit which is lower than the value set for RV. It appears that even the RD was faulty.
If one looks at the well known reactions of MIC, even without actually knowing the UC chemical processes involved for MIC manufacture and use, it is clear, that the MIC is highly reactive undergoing self addition reactions with its dimer and trimer forms and polymerization reactions in the presence of certain chemicals and water and if iron flakes were present either from corroded pipes, their entry would have helped in catalyzing the entire sequence of unwarranted reactions.
In the plant at West Virginia of UCC, the crucial pressure gauge are linked with an automatic warning system as well as the control room, unlike the under designed UCIL at Bhopal which had first of all pressure gauges which were manually operated and secondly neither a control room or an automatic warning system was incorporated in the factory.
Apart from inadequate maintenance and under designing of the safety systems, dependence on manual operations was a major setback. It is evident that the company’s sole aim in India was for making profits at the expense of safety of workers and the public.
8
The UCIL’s financial status before the disaster.
In 1981, the Imperial Chemical Industries (ICI), were licensed to sell synthetic pyrethroids in India. It was quite evident that UCIL would lose its market for Sevin; hence, the company resorted to unethical strategies to prevent the manufacture of pyrethroids. This did not work, as the company was not able to furnish details to show pyrethroids were dangerous. The market for Sevin began to shrink. Futher, the
Bhopal plant which was designed for a production of 5000 metric tons of pesticides per year, never came any where close to this target. It production decreased from about 2500 metric tones in 1982 to approximately 1500 metric tons in 1983 and in 1984, even less than 1000 metric tons. The company was losing money rapidly, and in 1984 showing a loss of about 4 million US $ (David Wier, 1986).
It appears that for the best interest of UCIL, it should wait for a disaster to occur and thereby escape from its existing financial problems, evade compensation, as the enforcement laws that existed in the country, were easy for UCIL to flee.
Compensation!
The biggest issue after the Bhopal gas disaster was the question of compensation. The total gas affected were 5,00,000 and among them, 3300 died immediately. In any disaster, the most important relief to the victims is compensation. Thereby, the affected individuals can once again begin their day-to-day chorus. Since, the amount to be compensated, is always a time consuming legal battle, the victims are at the mercy of the company. Unless, an interim relief is provided to the victims, the other problems that are offshoots of a disaster would arise. All countries proceed initially with an interim relief. Many lives of were shattered due to negligence by the government and Union Carbide Corporation. Many had lost their bread - winners, source of livelihood, children had become orphans and those who survived were the “living deads”. Many were incapacitated, unable to work any more due to poor health because of the toxic gas exposure. Their lungs were damaged permanently, had neurological and acute psychiatric problems, in addition to host of other health problems.
At this crucial juncture, the no interim relief was provided to the helpless victims.
Initially, compensation for the disaster was around 3,300 million dollars, which was not a substantial sum taking into account the magnitude of the disaster. However, the final settlement was for a paltry sum of 470 million dollars, which is equivalent to Rs.
715 crores. The Supreme Court, the highest court in the land, had ridiculed itself. The
Court had chosen itself to shield the government. It appears that the existing government had maneuvered justice and the Court a party to sacrificing the interests of the Bhopal gas victims to a need of creating a congenial atmosphere for other multinationals to invest in India. A leading legal expert and a former Vice Chancellor,
Dr.Upendra Baxi commented, “ the instruments of justice have themselves become instruments of injustice”.
9
For Union Carbide there was no happier moment than this verdict. If such a disaster had occurred at
West Virginia, the site of Union Carbide Corporation, the compensation would have been around 10 billion dollars, which is more than the entire worth of the Union Carbide Corporation.
The settlement costs for Union Carbide was only 50 cents per share as the major portion of the 470 million dollars was coming from its insurance cover. The Union Carbide had made a profit of 720 million dollars in 1988 and it had only to draw 70 million dollars from this profit to settle for 470 million dollars. The Union Carbide’s shares increased by 2%, in the stock exchange market, as a result of the decision. India became a safe haven for all Multinationals!
Table 1: Indicates the compensation paid by other companies after disasters.
Company
Manville
Corporation
A.H. Robbins
Number people affected of Health damage
Total compensation
(in dollars)
138 million
470 million
Average compensation
Per head
(in rupees)
6.32 lac
La Roche
Union Carbide
60,000
9400
37,255
500,000
3300 deaths
Cancer &
Asbestosis
Pelvis &18 deaths
Uterine disorders
Skin, genetic problems multi-organ lung damages
2500 million
520 million 8.41 lac
5.63 lac
0.15 lac
(Rs 15,000.00)
The cost figures in the above table, speaks about the posture taken by the company towards compensation. Only a sum of rupees 15000 equivalent to 940 dollars per individual was the settlement made by the Supreme Court of India with the Union Carbide Corporation for a lifetime disability of the victims. The court had made no attempts to calculate the costs incurred or expected to be for medical treatment and loss of an earning member or other unforeseen costs. Yet this is what the Chief Justice of the Supreme Court, Justice Pathak had to say “a just, fair, equitable and reasonable sum”.
This itself spoke volumes ...
A mockery of the Indian judicial system!
Post Disaster Era!
The Bhopal gas disaster drew worldwide concern, as it was a case of criminal negligence by a giant multinational company. Scientists all over the globe were startled by the deadly impact of the gas and were keen to carry out research on various aspects of MIC poisoning. Bhopal had become a guinea pig for the rest of the world.
The focus was on chemical behaviour and toxicity of MIC as very little was known or made available earlier. Although, Union Carbide aware of every aspect of the danger of MIC, it however was a classified information. It is understood from the British Information Services, the Union Carbide
Corporation was involved in research in atomic uranium, war gas or chemical warfare research and agricultural research. Many countries viewed the MIC gas as a potential prospect for their chemical
10
warfare. programmes. Others used the gas disaster for advanced modeling and simulating experiments to upgrade their pre-existing information on chemical warfare.
In India, the Central government had sanctioned major projects to study various aspects of the disaster.
The Indian Council of Medical Research (ICMR), report was not made public. Those who had managed to get their hands to the report, found it an extremely poor designed, inferior quality research output, meant more to somehow use the grant rather than see the whole issue for the benefit of the existing survivors (see Table 2).
11
TAXPAYERS MONEY GONE UNACCOUNTED!
ICMR PROJECTS ON BHOPAL GAS DISASTER - RUPEES 5 CRORES AND 59 LACS -
HOW MUCH WAS A SHAM?
The Indian Council of Medical Research conducted major research projects to study the impact of the gas disaster on human health (ICMR, Report – 1990,92). A total of 25 projects on human health impacts were initiated from 1985. The amount spent till September 1991 were at the tune of 5 crores,
59 lacs and 880 rupees. In 1991, sixteen of these were being continued and the remaining concluded. A number of these projects were poorly conceived, ill planned and designed without foresight, no accountability as projects were even stalled because of personality clashes or unavailability and instrumentation problems.
Table 2: A few of the projects undertaken by ICMR after the Bhopal disaster .
S.No.
1.
2.
3.
4
5
6
7
8
9
Name of the projects
Long term epidemiological studies on the health effects of toxic gas exposure through community health clinics
Studies on clinical and forensic toxicology of
Bhopal Gas Disaster.
Budget
(Rupees)
Time frame
65,23,000. Feb1985, and completion
March
1994.
Establishment registry at Bhopal.
Studies on
Alveolar lavage lung chambers
Immunological of population based cancer
Follow up to see Corneal opacity in gas-affected areas.
Studies on lens proteins in cataract.
Broncho
Radiological spectrum of
Chromosomal aberrations in Individuals exposed to MIC
Outcome
Abortion rates are still higher in exposed areas;
Morbidity is still on the rise.
Status
26,57,632.
77
14,52,553
22,39,167.
00
9,55,566
2,04,110
Feb 1985, till Sept
1991.
Oct for rupees till 1991
March
1986 to
Sept 1991.
Nov 1986 to
1991
1985
Sept
Feb1985 to
Sept 1991
Project has been stalled because of problems between
Principal
Investigator and
Administrative head
No evidence to suggest or rule out role of gas exposure causation in of cancer.
Corneal opacity was more in affected areas.
Methods not sensitive enough for studies
Macrophagic alveolitis after 3 years of gas exposure. Cases of Chronic bronchitis is on the rise
Recommended for continuation till March 1992 review committee.
Recommended for continuation till March 1992 by review committee.
Staff gone to court.
Extension requested
Review committee terminated work
17,02,539
31 lacs
Feb 1985 to
1991
Sept
60,67,680 April 1986 to Sept
1991
Pathogenic abnormalities observed
No results as frequent changes in Principal investigator.
June 1985 Most
Review recommends termination
Review committee recommends termination work Review
12
10
11
12.
13.
14 parameters
Mental health studies in
MIC exposed population
Organic brain damage - a pilot study
Genetic risk evaluation on pregnancy outcomes.
Oral, mucosal, gingival and orodental anomalies in mothers were exposed
Study children of whose pulmonary effects of toxic gases to children
15,44,800.
00
1,49,140.0
0
35,98,226.
00
5,16,210.0
0
23 lac contributed from outside country the
Aug1985 Recovery with passage of time
Dec1989 to
1990
Sept 1985 to June
1991
Sept
Feb 1985 to June
1991
Nov 1986 to
1991.
June
Localisation brain observed of damage
Sample size was too small for interpretation
Obstructive lung diseases in 15.4% in affected children as compared 8.3% control. committee recommends termination
Review committee recommends termination
Review committee recommends termination
Review committee terminated the work
Review committee asked the team to submit fresh proposal.
Review committee terminated the work
The report was an another example of how taxpayers money was misused in conducting research which except for a few, had no clear cut objectives and no one accountable for the output of the work. A few institutes under the Council of Scientific and Industrial Research (CSIR), for instance National
Environmental Engineering Research Institute (NEERI), Nagpur and Indian Institute of Toxicological
Research (ITRC), Lucknow, carried out environmental and human health. ITRC dispatched a team of experts immediately after the gas disaster as a relief team to treat the gas exposed victims. NEERI conducted environmental surveys around the UCIL premises (NEERI-Report, 1995). NEERI investigated the impact of indiscriminate disposal of wastes by UCIL on the land and water environments. The work was initiated in 1993 and the NEERI executive summary which was available on Nov. 1995, focused upon contamination in the UCIL premises and had no mention on contamination at the residential areas around the UCIL. This was only the first phase of the work, while the second phase could only begin after the Madhya Pradesh Pollution Control Board get legal permission from the court.
It is well known that Madhya Pradesh Government, had licensed the Union Carbide India Limited, and permitted it to be located within a crowded neighborhood.
The responsibility of the gas disaster lay between the Madhya Pradesh government, Union Carbide
Corporation and the Indian operators of UCIL. However, neither of the parties was ready to take the responsibility of the disaster. In the midst of all this confusion, a proper compensation was not being awarded to the victims. If the Madhya Pradesh government undertook any environmental surveys through government agencies, then the design, test results and priority of surveys could be modulated, manipulated and tailored according to the governments needs so as to marginalize its role in the disaster. Hence, an independent agency to carry out the survey would be an ideal solution.
13
In 1999, Greenpeace International carried out surveys in order to gain an insight into the nature and severity of chemical contamination (Grrenpeace,1999). Greenpeace analysed samples of solid wastes, soils and groundwater within UCIL and its surrounding areas. Greenpeace found samples to be contaminated with volatile organic compounds and heavy metals. It is beyond doubt that test report available from Greenpeace was an unbiased and an outstanding one. However, the survey did not include human samples.
The Fact Finding Mission of Bhopal Gas Disaster
Bearing this in mind, a Fact Finding Mission (FFM) for Bhopal gas tragedy, was publicly launched in
November 1998 with a mission to carry out an exhaustive study so as to bring out ample evidence in order to give a fairer deal in terms of compensation for the rehabilitation of the gas victims. The FFM has focused on different teams to contribute on different aspects viz. medical, environmental, economic, legal and social in its study, so as to strengthen its claim for compensation for the gas victims.
The FFM started with a common questionnaire from December 1999 that was meant to be a broad survey for gathering basic information that could be used by all the teams involved in FFM. A sample size of approximately 4000 was collected from 27 of the 36 gas affected wards in Bhopal. Ms. Archana
Aggarwal, a researcher from Jawaharlal Nehru University (JNU), Delhi, volunteered to conduct a detailed analysis of the data after an initial primary analyses by Ms. Leena of the Central Coordination
Committee of FFM.
The Medical Care and Rehabilitation, which comprised essentially doctors and scientists working upon human health problems post disaster era.
The Medical Research team headed by Dr. Antanu Sarkar is to consolidate and analyse scattered data carried out by government, private and other agencies and assess the health status of the gas victims. It also included developing a strategy to conduct long term monitoring of health gas victims. Dr. S.
Mudgal, an occupational health specialist, is to analyse the medical research data and fill in the lacuna in the report.
Dr. Amit Basu, researched the mental health consequences and the cultural impact of the gas victims.
The focus is on psychiatric problems, like anxiety, sleeplessness, depression, lack of concentration, motivation, impaired memory, irritability, dizziness and other issues related to a disaster.
Environment work by Dr. Amit Nair, an environmental scientist, would conduct environmental assessment in and around the UCIL premises. He would survey and screen the environment and humans for possible chemical contamination.
Economic rehabilitation would be undertaken by Mr. David Selveraj so as to understand the current status of economic rehabilitation.
Social rehabilitation would indicate an overall socio-economic status and would be done by Dr. Veena
Das, professor, JNU, Delhi.
Mr. S. Muralidhar, a lawyer at the Supreme Court of India, would pursue legal aspect. He would have to battle out with all the information available from different teams, for a better compensation for the victims.
14
Mr. Sukumar Murlidharan and N.K. Singh would coordinate Media coverage in English jointly while the Hindi coverage by Mr. Narendra Mouriya. Mr. N. Rajan, a
Key Bhopal journalists during the gas disaster would provide his expertise for the media coverage.
Survey on Human and Environmental Contamination around UCIL.
The most important task prior to assessment of human and environmental contamination would to be scrutinize the UCIL’s inventory for toxic chemicals.
Ascertain if, few of these chemicals they would still exist in the environment.
The fate and behaviour of a chemical in an environment is its intrinsic property. It depends upon the constituting elements and the bonds that exist between them and the nature. The physical property like solubility, volatility, boiling point, melting point as well as chemical properties such as reactions in air, water and in different environmental factors depends upon the intrinsic property, characteristic to it.
The UCIL inventory indicates a wide spectrum of compounds that were reactants, catalysts, byproducts or the end products. It would be a futile task to test for each of them since; many would not be present because of their short half-lives or would be transformed into other harmless products by natural environmental conditions. It would be worthwhile to consider those chemicals, which are toxic and also persistent i.e., remain over long periods of time in the environment.
In the present environmental and human contamination survey, the presence of a few Heavy metals,
Pesticides and Volatile Organic Carbons (VOC’s) in samples were investigated.
1. Heavy metals : A total of four heavy metals were tested in the samples. These are a). Mercury (Hg) b). Lead (Pb) c). Chromium (Cr) d). Nickel (Ni)
15
2. Pesticides : HCH (BHC) isomers, like gamma-HCH (Lindane), alpha- HCH, beta-
HCH were considered.
Note : Sevin (carbaryl) and Temic (aldicarb) were not considered because of their short half-lives in the environment.
3. VOC’s : Dichiorobenzene, 1,3,5-trichlorobenzene, trichlorobenzene and tetrachlorobenzene,
1,2,4-trichlorobenzene, 1,2,3-
The need for an environmental survey!
The factory started operating from 1969 and till 1977 it used dump all effluents in an open pit near the eastern wall of the factory. Then onwards most but not all, effluents used to be discharged into the two solar evaporation ponds (SEP), behind and outside of the factory. The solar evaporation ponds were spread in an approximate area of 22 acres. The lime pit effluents and other organic wastes were discharged into the evaporation ponds. The evaporation ponds were lined with a film of polythene to prevent seepage. However, one should not overlook the fact that polythene sheet are not corrosive proof and a wide spectrum of chemicals present in the effluents, like acids can easily destroy their structure.
The UCIL had two lime pits 28 feet in length X 12 feet breath X 12 feet D* each having two compartments. The primary neutrilization pit of a size 22 feet X 12 feet X 12 feet and the secondary neutralization pit of 6 feet X 12 feet X 12 feet were separated by a concrete wall. Hydrochloric acid is pumped to the lime pit for neutralisation and the effluents from here go to the evaporation pond.
Although, the UCIL management insists that the spent lime is replenished, that after every time acid is neutralised, some lime is used up in the process, this cannot be ascertained.
In rainy season, these effluents used to overflow and enter into sewages that used to pass through J.P.
Nagar, a slum cluster opposite the main gate of the factory.
It has been 17 years since the closure of the factory, but still the hand pump and the community water have a strong stench of organic solvents. An organisation by the name of Bhopal Group for Information and Action (BGIA), contacted different research organisations to test the water samples, but their request was turned down since, the testing of sample, required clearance from the State government.
The Citizens Environmental Laboratory, Boston, USA agreed to test the water and soil samples from
J.P. Nagar. The report indicated high levels of dichlorobenzene and pthalates in the samples. The toxicological effects of dichlorobenzene include damage to liver, kidney and respiratory system while pthalates are toxic to liver.
The studies clearly indicate that there is a definite contamination problem around the residential areas surrounding the factory.
Hence, there is serious environmental problem lurking around the UCIL factory that has to be assessed, evaluated and if possible remedied with available technologies at the earliest!
Environmental survey.
16
The Fact Finding Mission felt that the claim for an appropriate compensation to gas victims could be consolidated if inputs on the prevailing environmental contamination around residential areas could be established with UCIL factory.
In order to prove this point, it would be necessary to know what type of chemicals were used in the factory and what were the end products suspected to be present in the effluents.
Chemicals dumped within the factory premises.
The UCIL workers with more than 10 years experience of working in the factory reported that the following chemicals (Table 3) have been dumped within the factory premises by the factory management.
Table 3: Chemicals dumped in the factory site .
Chemical
Alpha-napthol
Chloroform
Carbon tetrachloride
Methanol
Methylene chloride
Mercury
Ortho-dichlorobenzene
Sevin
Use
As slurry and dust
Solvent in MIC plant
Solvent in Sevin plant
Solvent in Temic plant
Solvent in Temic plant
Sealant in Pan filter
Solvent in Napthol plant
As slurry and dust
Dumped amount in MT
50.00
100.00
200.00
10.00
50.00
1.0
250.00
50.00
In April, 1996, the Indian Institute of Chemical Technology (IICT), Hydrabad and National
Environmental Engineering Research Institute (NEERI), Nagpur, presented their report on the basis of analysis of 2.5 kg sample collected from drums, bags and trolleys near cycle stand godown and soap stone godown.
Table 4: Metals detected in Sevin and alpha-napthol waste*
Metals
Cadmium
Chromium
Copper
Lead
Manganese
Nickel
Zinc
Sevin waste (mg/kg)
1.247
26.8
40.64
22.26
487.25
20.85
28.73
Alpha-napthol waste (mg/kg)
Below detection limit
42.3
7.35
4.88
67.66
31.44
17.05
Table 5: Organic chemicals detected in sevin and napthol tar*
Organic chemicals Sevin tar (mg/kg) Napthol tar (mg/kg)
17
Volatile matter
Napthol content
3.07
12.1
2.83
23.18
* Analyses conducted by Indian Institute of Chemical Technology (IICT), Hydrabad.
It is worthwhile to mention that none of the analytical surveys conducted post Bhopal disaster, have shown the presence of the pesticides like Sevin and aldicarb were the final products of the factory.
Both, carbaryl and aldicarb is non-persistent compound, unlike organochlorines such as DDT and BHC
(HCH), and have short half-lives in the environment. Hence, testing for these chemicals would be a futile exercise unless data for this and a few other chemicals had been made available before the disaster (see Table 6).
18
1.
2.
3.
4.
5.
6.
7.
Table 6: Chemicals dumped by Union Carbide Management around the factory from 1969-84.
S.No. Chemicals Quantity
(MT)
Use in factory Nature of pollution
Aldicarb
Alpha-napthol
Benzene Hexachloride
Carbaryl
Carbon tetrachloride
Chemical waste tar
Chlorobenzoyl chloride
2.0
50.0
5.0
50.00
500.00
50.00
10.00
Product
Ingredient
Ingredient
Product
Solvent
Waste
Ingredient
Air, water & soil
Air & Soil
Air, water & soil
Air, water & soil
Air & water
Water & soil
Air, water & soil
20.
21.
22.
16.
17.
18.
19.
12.
13.
14.
15.
8.
9.
10.
11.
Chloroform
Chlorine
Chlorosulphonic acid
Hydrochlroic acid
Methanol
Methylene chloride
Methyl Isocyanate
Mercury
Monochloro toluene
Monomethyl amine
Naphthalene
Ortho dichlorobenzene
Phosgene
Tri methylamine
Toluene
300.00
20.00
50.00
50.00
50.00
100.00
5.0
1.0
10.00
25.00
50.00
500.00
5.0
50.00
20.00
Solvent
Ingredient
Ingredient
Ingredient
Solvent
Solvent
Ingredient
Sealant pan filter
Ingredient
Ingredient
Ingredient
Solvent
Ingredient
Catalyst
Ingredient
Air & water
Air
Air & soil
Air & soil
Air & water
Air & water
Air, water and soil
Water and soil
Air, water and soil
Air
Air
Air
Air
Air
Air, water & soil
Source: Satinath Sarangi, Sambhavana Clinic, Bhopal
The factory became operative in December 1969 and since then till 1984, a major amount of chemical substances like pesticides formulated in the factory, initial reactants, byproducts, catalysts and other substances used, were dumped in and around
Factory premises. These toxic contaminants in the form of solid, liquid and gaseous products caused pollution in the soil, water and air in and around the factory. Till date, the soil, water and around the factory are polluted.
Dumping of chemicals .
Many toxic chemicals are still remaining within the UCIL factory site (see photograph) while others are dumped at the solar evaporation pond (see photograph) that is across the railway track. The UCIL had acquired land for the purpose of a landfill that lay across the railway track. It is understood that
19
toxic wastes were pumped from the factory to this landfill. In fact, this waste dump is present in the other side of the railway track, across the factory. To pump the effluents, it would require pipes to be laid under the railway track, which means it has to done with prior permission of the railway ministry and technically unfeasible to put anything under the railway track.
Objective of the Environmental Survey
The objective of the present survey is to investigate whether human population residing around the premises of UCIL are still exposed to toxic chemicals, and if so, which chemicals and to what extent.
There are three sinks in the environment through which chemical contaminants enter into living forms.
These are soil, water and air. The soil is the major sink, followed by water that transfers contaminants through different continents while the air is responsible for a rapid long distance transmission of most of these chemicals. Further, chemical contaminants present in the different compartments can easily migrate from one compartment into another and the aerial component.
The soil is a niche for a diverse type of living forms from microbes to plants, animals and human beings. When the soil is contaminated with chemicals, it is very likely that there would be a possibility of these chemical toxins to transfer themselves into the living components of the soil ecosystem. All types of living that thrive in the soil, such as earthworms; plants, reptiles, birds and human beings are exposed to these chemicals through the food chain. When water contains chemicals, it begins to enter into all living forms in water, like mollusks (snails), fish, amphibians, reptiles and water mammals present in the aquatic ecosystem. Similarly, living organisms thrive in atmosphere too, in addition to all live forms that depend upon oxygen for sustenance.
In the present survey, emphasis is on environmental contamination leading to contamination to human beings. With this in view, a pilot study taking soil, water, food and human milk.
A suitable indicator for human exposure to chemical contamination is analyse breast milk. The survey would not only indicate the type and levels of toxins within mothers but also show the immediate exposure of toxins to infants through the first breast-feed and subsequent feeds.
Material and Methods
1. Sampling sites.
The choices of areas were based upon its proximity towards the UCIL factory and the dumpsites close to the factory. In addition, the samples sites were taken in such a way that it was taken in terms of north, south, east and west of the factory (see figure - 2).
The following residential area site have included in the study:
1). J.P. Nagar. 2). Kanchi. 3). Nawab colony.
5). Anu Nagar. 6). Arif Nagar. 7). Ramgarh Colony.
4). Atal Ayub Nagar
8). Factory premises
2. Samples.
In order to investigate the environmental transfer of a chemical toxins, from environment to humans, it would be imperative to firstly detect and quantitate a few of these suspected chemical toxins in the environment and then ascertain if there is route for human exposure.
In this study, the following samples were tested for contamination. These include: -
20
1). Soil: - the levels in the soil would indicate availability of chemical toxins for living
forms.
2). Water: - It is an indispensable part of life and its contamination means easy access to chemical toxins to life forms.
3). Food samples: - chemical toxins trans-locate from soil to vegetables grown in
contaminated areas and becomes a contaminated link in the food chain.
4). Human breast milk: - contaminant levels indicate toxins for next generation.
21
22
3. Sample Collection.
Soil samples: A total of 14 samples were collected for the analyses, out of which 5 samples were from the factory site, while the remaining from the residential areas surrounding the factory site.
The residential areas include Anu Nagar and Nawab colony at the northern side of the factory, Atal
Ayub Nagar at the northwest; Kanchi at the northeastern side; J.P. Nagar at the southern side; Rajagarh colony at the eastern side and Shakti Nagar at the south eastern side.
The soil samples from the factory premises include two samples very close to the Sevin plant side, one from the cycle stand site, one close to the alpha napthol plant site and one from the solar evaporation tank which lies across the railway track.
The collections were based on random sampling method where five core sub-samples i.e. from four corners and a central point of a selected site represented a sample for a given area. An auger was introduced 3 inches deep from the surface of the soil to collect the soil sample from each sampling point. All soil samples were collected in transparent python bags, labeled and sent to the place of analyses. These samples were stored at -20
Centigrade, until extraction.
Water samples: A total of eleven water samples were collected from similar areas of soil collection. In residential areas, water sample were collected from hand pumps are used by the local population for drinking, bathing and washing purposes. The water samples were collected in Teflon capped 2.5 Litre brown coloured bottles, so that photolyis of light sensitive compounds in the water samples are brought down to minimum. In addition, a water samples were collected within the factory premises i.e. within the Sevin plant area and one from an open pond adjacent to the solar evaporation pond. Samples were transported to the laboratory, where it was stored in a deep freezer maintained at -20
Centigrade.
Food samples: In one of the residential areas, it was observed that the local population grew seasonal vegetables for their consumption. These include radish, brinjal and spinach like palak and meethi
(spinachs). Samples of vegetables were wrapped in foil and sent to the laboratory, where it was stored at -20
Centigrade.
Breast milk: A total of eleven milk samples were collected from residential areas adjoining the UCIL factory. All relevant details of the donor like age, number of previous deliveries, socio-economic conditions and a few more, were taken prior to collection of the samples.
Samples of breast milk were manually collected in 5ml Teflon screw cap Borosil vials and stored immediately at 0
Centigrade and transported in an ice box to the laboratory where they were kept -20
Centigrade, until extraction.
Note: The most difficult part of the survey was the collection of human milk samples. The project coordinator, Ms. Tejinder Birdi and the author, made all efforts at three major government hospitals to acquire breast milk samples. However, efforts were in vain since, according to the medical superintendent, the government had given strict instructions not to permit any individual/s or from private institutions, other than government agencies, to collect samples related to Bhopal gas disaster.
Mr. Sathyu Sarangi, from the Sambhavana Trust provided the milk samples with help of his staff.
4. Chemical Analysis of Samples
23
4.1. Anaysis of Metals.
The sample preparation depends to a large extent on the sample, its matrix and sample treatment which finally determines the accuracy of the procedure. All the samples were thawed prior to extraction. The analysis of metals from the sample, involves sample drying, digestion, extraction and finally the analysis.
4.1. Sample drying: Soil samples were dried prior to weighing and dissolution. Air-drying at
25
Centigrade is preferred method for soil as substantial loss of volatile elements, such as mercury, can occur at elevated temperatures. The water samples (10 ml.) were taken as such, without further processing. The plant materials were dried at 80
Centigrade as per standard recommended procedures for plant materials.
4.2. Digestion and Extraction: The total element in the sample requires complete and vigorous digestion with acids (Aqua regia a mixture of 3 Volumes of Nitric acid with 1 volume of Hydrochloric acid) for soil samples.
For the preparation of 10,000 ppm solution of soil sample, accurate weighing of 0.1 gm of the sample and add 5ml Aqua regia. The mixture is heated on a hotplate for 30 minutes, and later, cooled and filtered. This is made up to 100ml in a standard flask. This 10,000-ppm sample is further diluted to 100 ppm for actual analysis.
In the case of plant materials, the most satisfactory and universal digestion procedure adopted is the use of concentrated HNO
3
for digestion.
In breast milk samples, accurately weighing 0.2 grams of the sample and dissolving in 5 ml of dilute
HCL did preparation of 2000-ppm solution. The mixture was heated for 20 minutes and filtered through 42 Whatman filter paper. This 2000-ppm solution was used for actual analysis. The results are reported for 1000 ppm.
4.3. Analysis: The analysis was carried out in a Perkin Elmer model Inductively Coupled Plasma
Spectrometer (ICP-OES).
In the present survey, the presence or absence of four heavy metals were tested in the samples.
Inductively Coupled Plasma Spectrometer (ICP-OES) carried out the analysis of Chromium (Cr),
Nickel (Ni), Mercury (Hg) and Lead (Pb) directly from the extract solution.
Standard preparation: Commercial standards from Perkin Elmer of 10,000-ppm concentration were purchased. Multi element standards for ICP-OES analysis were freshly prepared keeping in mind that the elements to be analysed are compatible and are grouped together to avoid precipitation in the mixed solution.
Operating conditions for aqueous solutions: Machine used Integra XL single and dual monochromator.
The Integra XL is a fully computerized Inductively Coupled Plasma Optical Emission Spectrometry
(ICP-OES).
Table 7: The operating conditions of ICP-OES.
ICP - OES.
Power
Nebulizer type
Specifications
1000 Watts
Concentric
24
Plasma gas flow
Auxiliary gas flow (Argon)
Sample gas flow
Viewing height
Pump speed
10 L/min
0.7 L/min
0.4 L/min
8.0 mm
9.0 rpm
Result:
Among the four heavy metals analysed in the samples, Nickel was the most prevalent one. Five of the six soil samples showed nickel contamination while Chromium,
Mercury and Lead were present in three each and two samples, respectively. The table
8 indicates the concentration of heavy metals in the soil samples.
Table 8: Concentration (mg/Litre) of heavy metals in soil samples in residential samples around UCIL factory, Bhopal.
Location
Anu Nagar
Atal Ayub Nagar
J.P. Nagar
Kanchi Chola
Nawab Colony
New Arif Nagar
Chromium
-
-
1.131
0.7845
1.958
-
Nickel
1.628
-
0.2143
0.5779
2.3700
1.3990
Mercury
0.9798
2.429
-
-
-
1.2650
Lead
-
-
0.4667
-
-
0.3533
The soil samples in the UCIL factory were analysed from four different sites, since different types of chemicals reactions were confined to different areas within the factory. Soil samples showed the presence of Chromium, Nickel and Mercury.
Mercury were detected in significantly higher levels in the samples collected from the alpha-napthol site and below the Pan filter site. Nickel was present in four of the five sites within the factory premises while mercury was present in two sites at almost similar quantities, but their levels were comparatively high. The table 9 indicates the concentration of heavy metals in the soil samples.
Table 9: Concentration (mg/Litre) of heavy metals in soil sample within the UCIL factory.
Location Chromium Nickel Mercury Lead
Pan filter area - 1.1090 1.8160 -
0.0206 4.7660 - - Sevin Cycle shed
25
Sevin Plant -
Outside - 1
Sevin Plant -
Outside - II
Alpha-napthol plant site
Solar Evaporation
Pond
0.1520
-
-
0.5269
3.9350
4.6820
-
0.0065
-
-
1.8980
-
-
-
-
0.2767
Among the ten ground water samples collected from the residential areas, all samples contained Chromium and Nickel, while Mercury was present in six water samples and
Lead in eight water samples. Nickel was the predominant contaminant in water, with an average of 1.0990 ppm, followed by mercury, chromium and lead whose average levels were, 0.567, 0.026 and 0.122 ppm, respectively. The table 10 indicates the concentration of heavy metals in the ground water samples.
Table10: Concentration (mg/Litre) of heavy metals in hand pump water
Location
Anu Nagar
Hand pump - 1
Chromium
0.0056
Nickel
0.9036
Mercury
0.2576
0.0107 0.7804 0.2939 Anu Nagar
Hand pump - 2
Atal Ayub Nagar 0.0117
0.0149
1.8750
0.7447
-
- J.P. Nagar
Hand pump - 2
Kanchi Chola
Nawab Colony
New Arif Nagar
Rajgarh Colony
Solar Evaporation
Pond – Pond
Water
Shakti Nagar
0.0210
0.0095
0.0057
0.0143
0.0116
0.0126
0.9417
1.8000
1.0800
0.7932
0.1861
0.7155
-
-
0.1197
0.0264
0.0343
0.0317
Lead
-
0.0013
-
0.0497
0.0548
0.0117
0.0398
0.0413
0.0321
0.0113
All the three vegetables samples grown at J.P. Nagar, showed Chromium and Nickel, while Spinach showed Chromium, Nickel, Mercury and Lead. The levels of mercury found in Spinach were significantly higher any of the other metals present in the
26
vegetables. The table 11 indicates the concentration of heavy metals in the vegetable samples.
Table11: Concentration (mg/Kg) of heavy metals in a few vegetable samples grown at a residential area opposite the UCIL factory.
Vegetables
Brinjal
Chromium
0.1541
Nickel
0.3869
Mercury
-
Lead
-
Radish
Spinach
0.1130
1.1370
0.1169
1.2840
-
2.5100
-
0.5733
The predominant metal detected in the breast milk samples was Lead and was found in seven of the eight samples analysed. Chromium was absent in the breast milk, while Nickel and Mercury were present in two and three samples, respectively. The mean levels of Lead were marginally higher than Mercury, although Mercury was detected in fewer samples compared to Lead. The table 12 indicates the concentration of heavy metals in the breast milk samples.
Table 12: Concentration (mg/Liter) of heavy metals in breast samples collected from residential areas adjoining UCIL factory.
Location
Atal Ayub Nagar
Chromium
-
Nickel
-
Mercury
-
Lead
0.0380
J.P. Nagar
J.P.Nagar
J.P. Nagar
Kanchi Chola
-
-
-
-
0.0581
-
-
-
0.0550
-
0.0550
-
0.0454
0.0801
0.3135
New Arif Nagar
Rajgarh colony
-
-
-
-
-
0.6665
0.1517
0.0643
Shakti Nagar - 0.5235 - 0.2830
4.1. Anaysis of Chlorinated Compounds.
Pesticide analysis was carried out in a Gas-Chromatograph (GC), Perkin Elmer Autosystem XL. Each sample was analysed twice and the reproducibility of results was almost 90% by the above methods.
Recovery studies were performed separately for two soil samples and the results showed recoveries exceeding 90 percent for all the twelve pesticides. Recovery % for HCH was around 87-90%.
The pesticides chosen for study were obtained from RDH Laborchemikalien GmbH & Co. KG D-
30918 Seelze via Promochem India Pvt. Ltd, Bangalore India.
-BHC was 99% pure and all the other pesticides were above 99.6% purity level.
The following pesticides were analysed organochlorines.
27
1.
Beta- BHC (1,2,3,4,5,6-hexachlorocyclohexane)
2.
Gamma- BHC (1,2,3,4,5,6-hexachlorocyclohexane)
3.
Dichlorobenzene
4.
Trichlorobenzenes 1,2,3-, 1,2,4-, & 1,3,5- Trichlorobenzenes.
5.
Tetrachlorobenzenes
6.
Chloroform
7.
Dichloromethane
Temperature
1. BHC: 220C to programming
270C at a ramp
2. Chlorinated compounds: 40 to 70C at a ramp of 2C per minute, of of
Soil:
2Cper
GC: minute
For the pesticide analysis, each soil sample size taken was approximately 500g, out of which representative sub-samples in triplicate (35g) were randomly taken for the analysis. The pesticides were extracted for 8-10 hrs at the rate of 4-5 cycles per hour, in 150 ml of 50%(v/v) acetone in hexane in a Soxhlet extractor (Thao et al.1993b,
EPA method 3540). The extract obtained was cooled, filtered and concentrated in a rotary evaporator. The concentrate was again extracted in hexane/water with the help of a separating funnel and dehydrated by passing through sodium sulphate. The solution thus obtained was filtered and concentrated to approximately 5ml. The fractions obtained on with 20%(v/v) dichloromethane in hexane were analysed for the presence of twelve pesticides, by GC equipped with a split – splitless injection port and selective electron-capture detector (ECD). This detector allows the detection of contaminants at trace level concentrations in the lower ppb range in the presence of a multitude of compounds extracted from the matrix to which these detectors do not respond. The column used was PE-17, length 30m, ID 0.25mm, and film 0.25mm with a 2ml/min flow. The carrier gas and the makeup gas was nitrogen employing the split mode. The oven temperature was kept at 190
C to 280
C with a ramp of
5
C/min. The samples were calibrated (retention time, area count) against 1 and 10ppm standard mixed solution of all twelve pesticides. Each peak is characterised by its retention time and the response factors in ECD. Sample results were quantitated in ppm automatically by the GC software. The detection limit was 0.001mg/kg for organochlorines and 0.01mg/kg for organophosphate pesticides.
Recovery studies were performed separately for three original sample types by spiking the samples with known quantities of different pesticides and subjecting them
28
to similar analytical procedures. The average recovery was almost 92.8% for organochlorines and 89.1% for organophosphates. The reproducibility of results for all the pesticides was 95.8% and above for all the samples. However, the mean average reading of a particular type of sample analysed in duplicate, was considered.
One GC injection (30 min) of 5
l covered all twelve pesticides included in the analysis. Hamilton micro syringe injection of the pesticide dissolved in hexane as solvent were made directly onto the coated silanized column solid support, thereby eliminating the possibility of catalytic degradation by metallic surfaces. Pesticides were identified according to their retention times. The actual relative retention times for the different pesticides were compared with unknown samples. The multi-residue method that can detect twelve pesticides in one analytical run was preferred. This method is characterised by a broad scope of application, good recoveries and sensitivity and low solvent consumption, coupled with good analytical quality control.
Milk, Water and Vegetable extraction:
Weigh the milk sample and extract with 5-6 drops of 10% Sodium chloride solution and 15%
Dichloromethane (DCM) in hexane. Collect the organic layer and extract the aqueous layer twice again. Mix all the three organic layers, add Sodium sulphate to it, filter and evaporate the solvent. In order to evaporate the residual DCM, add some hexane in the RB and evaporate twice. Finally make up the volume to 5ml with n-hexane. Pesticides in milk and vegetable were extracted in a method followed by Kumari and Kathpal, 1995; Nair et al, 1996 and Madan etal., 1996.
Results:
The total HCH (BHC) pesticide concentrations in the six soil samples were 9 mg/Kg.
The average value of its concentration was 1.60 ppm. Among the six residential areas,
J.P Nagar had the highest level of the pesticides HCH with a level of 5.038 mg/Kg
(ppm), while Nawab Colony, Atul Ayub Nagar had almost similar levels, exceeding slightly over 1 ppm. Among the HCH isomers, the proportion of gamma- HCH exceeded those of beta- HCH. The table 13 indicates the concentration of pesticides in residential areas around the factory.
Table13: Pesticide HCH (BHC) in soil samples around residential areas adjoining
UCIL factory premises.
Location
J.P. Nagar
Kanchi
Beta - HCH
0.2263
0.3697
Gamma -HCH
4.812
0.2208
29
Nawab Colony
Atal Ayub Nagar
Anu Nagar
New Arif Nagar
0.0555
0.0014
0.0180
0.0404
1.7181
1.0633
0.0770
1.0265
Among the four sites in the factory premises, the HCH levels were highest at the
Sevin Shed. The total HCH in this area was about slightly over 8 mg/Kg (ppm), which was five times more than those present in Sevin plant site-I. The Solar Evaporation
Pond, which was dumping site outside the premise showed very low levels of the
HCH isomers. The table 14 indicates the concentration of pesticide HCH in the factory premises.
Table 14: Pesticide HCH (BHC) in soil samples within UCIL factory premises.
Location
Sevin Shed
Sevin Plant - I
Sevin Plant - II
Beta - HCH
0.0035
0.3101
0.0897
Alpha-Napthol Site 0.0041
Solar Nil
Evaporation
Pond *
Gamma -HCH
8.2814
1.3777
0.0359
0.0663
0.0358
* Acquired by the UCIL factory outside the premises of the factory
The total levels of HCH isomers in Brinjal and Spinach were almost similar. The gamma- HCH isomer exceeded those of beta-HCH isomer. The table 15 indicate the pesticide HCH in vegetable samples grown close to the UCIL premises.
Table15: Pesticide HCH (BHC) in vegetable samples around residential areas adjoining UCIL factory premises .
Vegetables Beta- HCH Gamma- HCH
Brinjal
Spinach
0.0033
Nil
0.0294
0.0215
The total concentrations of the pesticide, HCH in the ground water samples from the residential areas were 0.0898 mg/L (ppm). The mean levels detected in water were
0.011ppm. Water samples from Anu Nagar and Shakti Nagar were most contaminated with the pesticide HCH, while the other areas had almost similar levels. The table 16
30
indicates the pesticide HCH in ground water samples adjoining the UCIL factory premises.
Table 16: Pesticide HCH (BHC) in groundwater samples around residential areas adjoining UCIL factory.
Location
Anu Nagar - II
Atal Ayub Nagar
J.P. Nagar
Kanchi Chola
Nawab Colony
New Arif Nagar
Rajgarh Colony
Shakti Nagar.
Beta - HCH
0.0256
0.0016
0.0003
0.0005
0.0001
0.0016
0.0005
0.0336
Gamma -HCH
0.0146
0.0011
0.0015
0.0027
0.0012
0.0014
0.0004
0.0031
The water tested from the factory premises showed 0.115 ppm of the pesticide HCH.
This was ten times more than those present in the residential areas around the factory.
The table17 indicates the pesticide HCH (BHC) in water samples within the UCIL premises.
Table 17: Pesticide HCH (BHC) in water samples from the UCIL factory premises.
Location Beta - HCH Gamma -HCH
Sevin Plant Site 0.1050
Solar Evaporation
Pond – Water*
0.0010
0.0104
0.0175
* Acquired by the UCIL factory outside the premises of the factory
Among the residential areas, J.P. Nagar showed the highest contamination of Volatile
Organic Compounds (VOC’s) followed by Kanchi Chola, which showed 7.5 times lower than those of J.P. Nagar. Dichlorobenzene was the predominant contaminant in most of the cases. The total VOC level found in the soil samples were 5.86 mg/Kg
(ppm) while their average was slightly lower than 1 ppm. Among the six soil samples,
Dichlorobenzene, 1,3,5-Trichlorobenzene and Tetrachlorobenzene were present in all the samples. The table18 indicate the VOC’s in soil samples adjoining the UCIL factory premises.
Table 18: Volatile Organic Compounds (VOC's) in soil samples in residential areas around UCIL.
31
Location Dichlorobenzene
J.P. Nagar 2.4961
Kanchi 0.1096
Nawab
Colony
0.1304
Atal Ayub 0.1294
Nagar
Anu Nagar 0.1419
New Arif 0.1637
Nagar
Trichlorobenzene
(1,3,5)
0.7447
0.4149
0.1678
0.0102
0.0135
0.0140
Trichlorobenzene (1,2,4)
0.6070
0.0156
0.0063
0.0127
Nil
0.0150
Trichlorobenzene (1,2,3)
0.1701
Nil
Nil
0.0117
Nil
Nil
Tetrachlorobenzene
0.1073
0.0053
0.0060
0.0339
0.0161
0.0463
Both the vegetables were found to contain VOCs. The dichlorobenzene was the predominant contaminant in the samples. The mean concentration of VOCs in the vegetable samples was found to be 0.132 mg/Kg. The concentration of VOC's was almost similar in both the vegetable samples analysed. The table19 indicate the
VOC’s in vegetable samples adjoining the UCIL factory premises.
Table 19: Volatile Organic Compounds (VOC's) in vegetable samples in residential areas around
UCIL.
Location Dichlorobenzene
Trichlorobenzene
(1,3,5)
Trichlorobenzene (1,2,4)
Trichlorobenzene (1,2,3)
Tetrachlorobenzene
Brinjal
Spinach
0.2653
0.2354
0
0
0.0082
0.0073
Nil
Nil
0.0124
Nil
All the soils tested for VOC’s in the UCIL factory were positive for VOC's. All the soils from the factory site showed Dichlorobenzenes, 1,3,5-Trichlorobenzenes, 1,2,4-
Trichlorobenzenes and Tetrachlorobenzenes. Among the four sample sites, the Sevin
Shed showed the highest concentration of VOC’s. The amounts of VOC’s in the other three sites were more or less similar. The total VOC content in the samples were
1.855 mg/Kg while the mean levels in the factory premises was 0.463 mg/Kg. The total VOC content in soils from the Solar Evaporation Pond was found to be 0.268 mg/Kg. The table 20 indicates the VOC’s in soil samples from the UCIL factory premises.
Table 20: Volatile Organic Compounds (VOC's) in soil samples in the UCIL
32
Location Dichlorobenzene
Sevin Shed 0.1613
Sevin
Plant-I
0.1292
Sevin
Plant -II
Alpha
Napthol
Site
0.1124
0.1212
SEP -Soil 0.1215
Trichlorobenzene
(1,3,5)
0.1974
0.1883
0.2143
0.2081
Trichlorobenzene (1,2,4)
0.0065
0.0044
0.0073
0.0056
Trichlorobenzene (1,2,3)
Nil
Nil
Nil
Nil
Tetrachlorobenzene
0.4711
0.0233
0.0046
Nil
0.1389 0.0074 0.0006 Nil
The concentration of VOC’s was highest in Kanchi Chola while a marginally lower level was found in Anu Nagar. In the other areas it were almost two to almost ten times lower than these areas. The mean concentration of VOC’s in the ground water samples the residential areas were found to be 0.050 mg/Kg. The table 21 indicates the VOC’s in ground water samples from the UCIL factory premises.
Table 21: Volatile Organic Compounds (VOC's) in water samples in residential areas around UCIL.
Location
Anu Nagar
Dichlorobenzene
0.0104
Trichlorobenzene
(1,3,5)
Nil
Trichlorobenzene (1,2,4)
Nil
Trichlorobenzene (1,2,3)
Nil
Tetrachlorobenzene
0.0007
Atal Ayub
Nagar
0.0008
J.P.Nagar
Kanchi
Chola
0.0094
0.0147
Nawab
Colony
0.0012
New Arif Nil
Nagar
Rajgarh
Colony
Nil
Shakti Nagar Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
0.0029
0.0015
0.0060
Nil
Nil
0.0002
0.0003
Nil
Nil
0.0001
0.0007
0.0002
Nil
0.0006
Nil
0.0002
0.0005
33
Water samples from the factory premises contained 0.0331 mg/L VOC’s while those from a water pond adjacent to the Solar Evaporation Pond contained 0.008 mg/L
VOC’s.
Table 22: Volatile Organic Compounds (VOC's) in water samples from the UCIL factory premise.
Location Dichlorobenzene
Trichlorobenzene
(1,3,5)
Nil
Trichlorobenzene (1,2,4)
Trichlorobenzene (1,2,3)
Tetrachlorobenzene
Sevin Plantditch
S.E.P
Nil
Nil Nil
0.0025
0.0058
0.0008
0.0002
0.0298
0.0007
All samples of breast milk showed the pesticide, HCH. The average level of the pesticide in the breast milk was 2.39 mg/Kg while the levels ranged from 0.179 to
11.44 mg/Kg. The breast milk sample from Shakti Nagar had highest levels for both beta and gamma – HCH when compared to the other samples. The table 23 indicates the pesticide in breast milk samples from the UCIL factory premises.
Table 23: Pesticide HCH (BHC) in breast milk samples in residential areas around the UCIL Factory.
Location
Shakti Nagar
Beta - HCH
5.1367
Gamma -HCH
6.3345
Kanchi Chola
Rajgarh Colony
J.P.Nagar
New Arif Nagar
J.P.Nagar
J.P.Nagar
Atal Ayub Nagar
0.0376
0.1912
0.6947
0.0684
0.3271
0.0232
0.2317
0.1414
0.0915
0.0154
1.3580
0.6388
0.2343
0.1160
All samples of breast milk contained VOC’s. The total VOC content in breast milk samples was 17.12 mg/Kg. The 1,3,5 Trichlorobenzene was the predominant VOC and was present in all the samples. The sample from Shakti Nagar contained 9.52 ppm and was highest when compared to other samples. The average level of the VOC in the breast milk was 2.85 mg/Kg while the levels ranged from 0.588 to 9.52 mg/Kg.
The table 24 indicates the VOC’s in breast milk samples from the UCIL factory premises.
34
Table 24: Volatile Organic Compounds (VOC's) in breast milk samples in residential areas around
UCIL.
Location Dichlorobenzene
Trichlorobenzene
(1,3,5)
Trichlorobenzene (1,2,4)
Trichlorobenzene (1,2,3)
Tetrachlorobenzene
0.4690 02573 Shakti
Nagar
2.2693
Kanchi
Chola
Nil
Rajgarh
Colony
0.4580
J.P.Nagar
J.P.Nagar
0.3380
New Arif
Nagar
Nil
0.5221
J.P.Nagar 0.3514
Atal Ayub
Nagar
0.7016
0.6226
1.5986
0.2041
0.1993
2.1718
0.1800
0.0369
0.3826
Halo-organics: Dichloromethane and Chloroform.
5.8984
0.4120
Nil
Nil
0.7450
Nil
Nil
Nil
Nil
0.1354
Nil
Nil
Nil
0.0327
Nil
0.0386
0.0601
Nil
0.1094
0.0473
0.0574
Nil
Among the six soil samples from the residential area, Dichloromethane was present in all the samples. The levels ranged from 0.082 to 0.170 with an average amounting to
0.103. The soil samples from Kanchi Chola showed maximum concentration of
Dichloromethane and were almost twice more than most of the other areas. The other residential areas showed more or less similar amounts of this contaminant.
Chloroform was present in all samples and most of the soil samples contained this compound at fairly similar amounts. The average chloroform level in the soil sample was found to be 6.55 mg/L. The highest concentration of chloroform in Atal Ayub
Nagar was 6.77 mg/L while the minimum at Kanchi Chola was around 6.27 mg/L.
The table. Indicates the Dichloromethane and Chloroform in soil samples residential areas adjoining the UCIL factory premises. The table 25 indicates the Halo-organics in soil samples from the UCIL factory premises.
Table 25: Dichloromethane and Chloroform in soil samples around residential areas adjoining UCIL factory premises.
Location Dichloromethane Chloroform
35
J.P.Nagar
Kanchi Chola
Nawab Colony
Sevin Cycle Shed
Atal Ayub Nagar
Anu Nagar
0.0901
0.1700
0.0909
0.1790
0.0815
0.0995
New Arif Nagar 0.0877
6.5129
6.2668
6.5327
6.6593
6.7204
6.6237
6.6174
Soil samples within the factory premises showed both dichloromethane and chloroform . The chloroform in the samples in the factory exceeded those of dichloromethane. The chloroform and dichloromethane levels were almost similar in almost all soil sites in the factory. The average level of chloroform in the soil was 6.40 mg/Kg, which were 50 times more than dichloromethane.
Table 26: Dichloromethane and Chloroform in soil samples in the UCIL factory premises.
Location
Sevin Cycle Shed
Dichloromethane
0.1790
Chloroform
6.6593
Sevin Plant-1
Sevin Plant-2
Alpha Naphthol
Pan filter area
0.0809
0.1595
0.1177
0.1023
6.6299
6.4971
6.6826
5.5204
All the three vegetable samples analysed showed the presence of both
Dichloromethane and Chloroform. In spinach the dichloromethane levels were almost
30 times more than those present in either radish or brinjal. The average levels in the vegetable samples were 0.0284 mg/Kg.
The Chloroform was content was more in radish and brinjal when compared to spinach. The average chloroform content in the vegetables was found to be 7.51 mg/Kg, which were 264 times more than the mean levels of dichloromethane. . The table 27 indicates the Halo-organics in vegetable samples from the UCIL factory premises.
Table 27: Dichloromethane and Chloroform in vegetable samples around residential areas adjoining
UCIL factory premises.
Location
Spinach
Dichloromethane
0.0797
Chloroform
6.1843
Radish
Brinjal
0.0027
0.0027
8.2929
8.0403
36
All the eight ground water samples contained both dichloromethane and chloroform.
However, the dichloromethane levels in water were almost 2 times more than chloroform. Water samples from Rajgarh colony had the highest level of dichloromethane. The average concentration of dichloromethane was 1.63 mg/L.
The water samples from Atal Ayub Nagar showed maximum concentration of chloroform. The average concentration of chloroform in water was 0.85 mg/L.
The table 28 indicates the Halo-organics in water samples from the UCIL factory premises.
Table 28: Dichloromethane and Chloroform in water samples around residential areas adjoining UCIL factory premises.
Location
Anu Nagar
Dichloromethane
0.2580
Chloroform
0.9901
Atal Ayub Nagar
J.P. Nagar
Kanchi Chola
Nawab Colony
New Arif Nagar
Rajgarh Colony
Shakti Nagar
0.1065
0.1235
1.7250
0.3377
4.2690
4.6035
1.6660
1.3591
0.8013
0.3792
0.8544
0.8673
0.8650
0.6710
All the breast milk samples contained dichloromethane and chloroform. The amounts of chloroform were 3.2 times more than those of dichloromethane levels. The breast milk samples from J.P. Nagar showed highest levels for dichloromethane while maximum concentration of chloroform samples from New Arif Nagar. The average concentrations of dichloromethane and chloroform in breast milk were 0.359 and
1.154 mg/L. The table 29 indicates the Halo-organics in breast milk samples from the
UCIL factory premises.
Table 29: Dichloromethane and Chloroform in breast milk samples around residential areas adjoining
UCIL factory premises.
Location
Shakti Nagar
Dichloromethane
0.4109
Chloroform
0.9598
Kanchi Chola
Rajgarh Colony
0.0928
1.0896
1.3965
1.1541
37
J.P. Nagar
New Arif Nagar
Atal Ayub Nagar
0.1631
0.0864
0.3080
1.1337
1.4005
0.8785
The soil from the Solar Evaporation Pond, a dumping site for UCIL factory, showed both dichloromethane and chloroform. The chloroform levels were almost similar to those present within the factory premises.
The pond water samples adjacent to the Solar Evaporation Pond, showed dichloromethane and chloroform and their average concentration were 0.714 mg/L and 0.917 mg/L, respectively.
Table 30: Dichloromethane and Chloroform in SEP dumping site samples around residential areas adjoining UCIL factory premises.
Location
Solar Evaporation
Pond - Soil
Dichloromethane
0.0972
Chloroform
6.6141
Solar Evaporation
Pond - Water
0.7140 0.9165
38
Table 31: Summary of the analysis of chemical contamination around UCIL Factory and adjoining residential areas in Bhopal.
Heavy Metals VOC Halo-organics
Samples
Soil -
Residential
Areas
Chromium
0.647
(0.021 to 1.96)
Nickel
1.032
(0.007- 4.77)
Mercury
0.568
(0.980 - 2.43)
Lead
0.137
0.277 - 0.467)
Chlorobe nzenes
Dichloromethane
0.932
(0.1715
–
4.1252)
0.103
(0.0815 - 0.1700)
Chloroform
6.546
(6.2688 to 6.7204)
Soil-Factory 0.233 2.90 1.857 0.277 0.425
Ground water-
Residential to
0.026
(0.0013 to 0.0548)
0.006
(0.0015
–
0.0149)
0.128
(0.0809 –0.179)
1.636
(0.1065 to 4.6035)
6.4
(5.5204 – 6.6826)
0.849
(0.3792 to 1.3591)
Vegetables
Breast milk
0.012
(0.0057 to 0.021)
0.475
(0 to
1.137)
ND
1.099
(0.7155
1.875)
-
0.596
(0.9721 to
1.284)
0.097
(0.0581 to
0.5235)
0.057
(0.0264
0.2758)
0.837
(0 to
2.510)
0.129
(0.0550
0.6665)
0.191
(0 to 0.5733) to
0.149
(0.0380 to 0.3135)
0.132
2.854
(0.5883 –
9.5166)
0.028
(0.0027 to 0.0890)
0.359
(0.0772 to 1.0896)
7.506
(6.1114 to 8.2929)
1.594
(0.8755 to 1.4005)
Pesticides-
HCH isomer
1.605
(0.095 –5.0383)
2.041
0.011
(0.0009 – 0.0402)
0.021
2.392
(0.179 – 11.471)