Published by 
UNEP - United Nations Environment Programme
http://www.chem.unep.ch/pops/pops_inc/proceedings/Iguazu/AGNES.html


Environmental Contamination and Occupational and Urban Exposure to Hexachlorobenzene at Baixada Santista, SP, Brazil

by Ms. Agnes Soares da Silva

 

1 - Historical characterization of the problem

A chemical industry named Rhodia S/A located at Cubatão city, produced 82 tons of pentachlorophenol and 215 tons of the sodium salt of the same compound monthly, from 1966 until 1978. Also, 600 tons of chloridric acid as by product. 18 Polichlorinated-dibenzo-dioxins - PCDDs and dibenzofurans are always found as contaminants of these products and probably on the residues. 28 In 1974 the company started to produce 18.000 tons/year of carbon tetrachloride and perchloroethilene also.

The plant that produced pentachlorophenol and its sodium salt was closed in 1978 because of legal problems with the health risks and security to the workers. All of them were transferred to the other factory and have stable job life-long until retirement because of the health problems they had. Many of them had cloracne and organic and functional disorders of the liver. The connection between health problems and exposure was established by legal court. * Also, two workers died under conditions understood as occupational intoxication because of the dangerous process they were submitted during chemical manipulation at the factory.**

In 1993 the factory that produced carbon tetrachloride and perchloroethilene was also closed by Court decision through a document "determining the cessation of the activities of the industry in Cubatão until adequacy to human health..." A legal accord between Rhodia S/A, legal representation of the workers and the Public Ministry warranted tenure of four years for the worker’s job and health diagnosis and monitoring for the rest of their lives. The final decision is still under justice trial*.

Besides contaminating their own area, by dumping the waste on their backyard, Rhodia S/A disposed a large amount of the industrial waste out of the industrial area, in places not prepared for it, near urban areas, close to rivers or streams and to mangrove areas. Part of the residues were thrown away together with domestic waste in Pilões Valley, Cubatão, part near to Cubatão river and most part of it in Samaritá, the mainland area of São Vicente Island. A small amount was disposed in four different sites at Sítio do Coca, Itanhaém city, located just about 80 Km away south from the industry. (Figure 1 - Contaminated areas with organochloride residues at Baixada Santista, SP, Brazil)

The close estimate composition of the industry residues is 70 to 80% of hexachlorobenzene - HCB and 10 to 15% hexachlorobutadiene - HCBD. Tetrachlorobenzene, pentachlorobenzene, chlorophorm, perchloroethilene, carbon tetrachloride are also present but in smaller quantities. The presence of dioxins were not investigated on the residues. 38

 

Cubatão was considered a "national security area" during military government years of Brazil, what made it difficult and dangerous all kinds of questions about the policy for the industrialization of the country and any kind of non governmental organization. That’s the reason why the Environmental Protection Agency from São Paulo State, Cetesb - Companhia de tecnologia e saneamento ambiental, had the knowledge of this environmental problem since 197817 but only started to make a plan of acting on it after 1984, when community organizations in Samaritá denunciated the dumping sites to the State of São Paulo and started fighting for a solution. The first investigations were realized at Samaritá, outside of the factory, motivated by these organized communities. After the first results were publicized, the industry workers started to worry about their own chemical exposition and also started a process of investigation of the factory environment, and asked for their health risk assessment, what ended up with the shutting of the industry in 1993.

The sites with the most critical situation and the greater risk of environmental and human exposition are Samaritá e Vale dos Pilões. The first one for the large amount of residues disposed too close to urban, rivers and mangrove areas of the region. The second, because it is located near by a water source for most part of the cities of the Baixada Santista, upstream of the impound area of the State agency for water treatment and distribution - Sabesp. Also, because the area was occupied by small properties where the residents had subsistence activities, like bananas and vegetables planting or even small animals like chicken and pigs for small commerce or their own consumption.

The residents of Pilões were removed from the area at risk to a building constructed by the State Government, actually small apartments at another district of the city. The decision was taken by legal according between Public Ministry, the population of the site, the city hall and the State company for developing residences. There was a great social and psychological impact on the way of living of the removed population what caused much suffering. At Samaritá site the residences are still at the same place, very close to the hazardous sites. Instead of that, it is fast growing up, even after the publicity made about the environmental problems of the area. 29 40

To first start mitigate the impact it was built up a controlled disposal site with a waterproof impacted soil, clay and polyethylene canvas, to keep what was estimated to be 12.000 tons of toxic residues dumped at Samarita’s sites. This waste disposal contains now more than 35.000 tons of the residues mixture to soil and vegetables and there are much more on the soil to be cleaned. The weight excess increased the risk of rupture of the security layers and the scouring powder of the toxic to the environment. According to the local Manager of the Environmental Agency - Cetesb, one of the layers is already ragged and the scouring powder is being collected for final safe disposal. 29

Rhodia constructed also an incinerator at the Chemical Unit of Cubatão, at first to destroy the residues found in Samaritá 38 It started burning in 1987 and stopped in 1993 by judicial decision. The theoretical capacity of burning was around 50 tons/day of organochloride compounds and around 70.000 tons were burned during this time. It would probably take many years until burning all the waste disposed at Samaritá sites and at the industry, besides all of the others already known sites. Even though the incineration was pointed out as the best final solution to this case as far as technical knowledge and the law permits, because it reduces the amount of the waste and makes it less toxic and easier to final disposal, there are many doubts and controversy about incineration of organochlorine compounds. 22 The reason for that is because at urban and industrial cities, air pollution is of particular meaning for the high levels of contaminants and because of the complexity of the mixtures of gas and particles. Like a chemical reactor, all the pollutants may react amongst themselves with the sunlight as an energy supply.

The idea of incinerating is very simple: to use heat to break down organic compounds to get water and carbon dioxide. To achieve this objective is much more difficult than it seems. At high temperatures the compounds are broken down but they recombine as they go out of the chimneys and get the environment, may form even more hazardous compounds. These are products of incomplete combustion - PIC, and if they come from burned organochloride compounds they bring immediate and future risks because most part of them are carcinogenic, as dioxins and furans for example. 22

Cubatão is well known worldwide because of the air pollution due to concentrated industrial area located in a place that has natural barriers, geomorphologic aspects that difficult or obstruct the dispersion of pollutants.

Taking in account that the composition of the waste burnt is inconstant, soil, animal and vegetable organic residues and organochloride compounds coming from contaminated areas and that no one incinerator operates a 100% efficiency, part of what was burnt only changed the environment, from solid to the air. That’s the reason the incinerator at Rhodia industry could generate more problems than solution.

On the other hand, with no incinerating process a large amount of residues is still on the ground at Samaritá site and the Espera station that could be temporary is still untouched.

According to technicians from Cetesb in Santos, the scouring powder of the disposal site due to the rupture of one of the security layers should be incinerated together with the residues. When the incineration stopped, the industry was keeping the liquid in containers. In 1995 Rhodia was condemned on a trial and had to promote water containment and treatment of the sites before pouring to the streams and rivers of the region. Actually, during tests for the equipment for remediation, the industry used the water and poured it at Ribeirão das Areias stream, without legal permission for that and had to pay a fee for that.

The Brazilian Association of Technical Rules - ABNT, established that Rhodia residues are considered Class I - Dangerous ( they have one or more of the following characteristics: inflammable, corrosive, reactivity, toxicity and pathogenic ).35 Basiléia convention, Switzerland, 22/03/89 define as dangerous refuse "substances or objects that are to be eliminated or for wanting or need due to International rights" 27 At USA, the Law 94.580 21/10/76 classify dangerous solid waste all kinds of solid waste or a combination of solid waste that due quantities, concentration or physical, chemical or infectious properties, may cause increasing of morbidity or mortality rate, incapability or contribute to increase these parameters or present a considerable immediate or potential risk to human health or to the environment during its treatment, keeping, eliminating or managing inappropriately. 2 - 27

To classify the residues has a very practical and important meaning, the kind of care is needed to manage them and for their final disposal. On one hand is the quality of the residues what is really important, but on the other, it is also the quantity and the way of the disposal that will definitively influence on the level of health and environmental risk.

Recently final adequate destination of industrial residues started to be related with human health problems and to environmental damage due to contamination of fountains soil and air. 26 That’s the reason destining these residues is now being treated with more technical support, that is very fast developing to manage these risks.

In Cubatão city, during all the time the industry area was expanding, what happened on the 50’s years, there were no formal worries from the sanitary authorities or from environmental agency with the residues of the production, so, any solution had to be an industry’s solution. By that time there were no organized ecological groups or movement, only after 70’s years, so, these worries were not a social concern. The State institutions had no capability to control the situation because there was no political pressure for that.

In 1983, the State Environmental Agency, Cetesb, organized the information about industrial solid waste and found out Cubatão had 4.603.045,4 tons by year of solid waste, 38.650,3 tons of these waste being considered dangerous and 3.298.343,5, no inert waste. 16 "Rhodia’s case" is not an isolated problem neither is accidental, it’s only one among many cases that exist and must be investigated.

The first difficulty to evaluate human exposition to the residues was to find out an biomarker to measure it. 29 The prevalence of HCB in blood or human milk was chosen for the following aspects: the large mount of HCB on the residues, used for Cetesb as an indicator of the presence of other organochloride residues in soil, water and animal specimen. 17 There is methodology well known to recognize the compound under analysis, and the technique required is not invasive, being well established in human milk and blood serum. 34

As a matter of fact, HCB has never been used in our environment, not even as a contaminant of other pesticides, what makes the compound a good indicator of the exposition because it is no usual to find it in milk or any food, like it happens with DDT or HCH, frequently found in any research of the country. Its use was restricted and it is forbidden for any practice since 1989, Law 7802/89. 30

Lara et al, 1979 analyzed 44 samples of milk in São Paulo and found hexachlorociclohexane - HCH in all of them; pp’DDE, a DDT metabolite, in 95,4% of the samples. 88,6% had higher levels than it’s allowed by civil Law. 24 In 80 and 81 this study was repeated in pasteurized cow milk to study the impact of a more restrict legislation for organochloride compound; HCH and DDT and isomers were found in all the collected samples even though the levels became smaller; Dieldrin was found in a very small quantities 72% of these same samples. 24 Beretta and Dick also analyzed 68 samples of pasteurized milk in Porto Alegre - RS, in 1987; 97% had HCH total, 98,5% DDT and its metabolites and 85,3% had Dieldrin. 5

Schvartsman et al and Almeida et al, 1974, found DDT in total blood of the general population in São Paulo and Rio de Janeiro with the means of 42,6 ng/ml (São Paulo) e 336,0 ng/ml (Rio de Janeiro).36 Lara et al analyzed, in 1982, 25 samples of human milk in São Paulo and found HCH and DDT in all of the samples and Dieldrin in one of them .25 Willrich & Dick, in Porto Alegre, 1988, found organochloride in a based sample population: 55 analysis were realized, and DDT and its metabolites were found in a 100% of them, Dieldrin in 98% e HCH in 95%. Other organochloride compounds like HCB were studied but were never present.42 Costa et al found organochloride compounds in human milk and blood from urban and rural areas in Botucatu, Vitoriana e César Neto; human milk from rural areas were found to have 80% of the samples with HCH, 50% Aldrin e 30% de Dieldrin; urban district had 40% HCH, 40% Aldrin e 25% Dieldrin; on blood, rural area, 40% had HCH, 70% Aldrin e 70% Dieldrin and urban area 80% with HCH, 80% Aldrin e 60% Dieldrin. They made no considerations about HCB. 20

HCB presents bioconcentration, accumulates in fatty tissues, liver, kidney, pancreas and central nervous system, and there is a correspondence of level of the compound among these means, what make it easier to measure it even after years of exposition. 34 HCB also presents biomagnification, the more complex the living being on the food chain, higher must be the levels of the compound on the whole body burden. 21 -23 - 34

Besides that, HCB is of Public Health concern because it can induce Porphiria Cutanea Tarda, a well known pathology, there is experience on inducing cancer even though there is insufficient epidemiological information about human cancer induced by it. It spreads through many pathways, water, food, soil, vegetables and meat; it has been found in human tissues specially accumulated in fatty tissues; there is a possibility to avoid human exposure and prevent environment contamination. 34 - 41

HCB has a 4 years half-life under controlled conditions. To different compositions of the soil it may have no changes in a period of one year. It is very resistant to microbiologic biodegradation and it is totally insoluble in water. When found in water environment is absorbed by aquatic animals and plants and it becomes adsorbed to the sediments or may evaporate through the surface. 34

It is also possible to assume some exposure route to the population because Cetesb and the Rhodia S/a are monitoring HCB at the environment what shows different levels of concentration. Even though there are some questions about monitoring HCB in the water as an indicator of exposure and contamination because of its insolubility, the large amount involved makes it easier to identify the product.

Because it is persistent and accumulate in the fatty tissue, HCB can be a very good indicator or biomarker of the environment and for human exposure.

 

2 - Description, localization and composition of the hazardous waste sites - Rhodia S/A

Only three waste sites with Rhodia’s residues had been located until 1990, all of them in Samaritá, the mainland area of São Vicente city: one at a place named Quarentenário, between the Padre Manoel da Nóbrega main road at Km 67 and the railroad on the other side, nearby Mariana river and two others on the other side of the same road and the Branco river, at Kms 67 and 69. This is the main road to southern coast of São Paulo State, and that’s the reason everyone looked for new waste sites along this road. (Figure 2 - Baixada Santista and the hazardous waste sites from Rhodia S/A at Samaritá, São Vicente)

All the other sites were found outside of this area after 1990, four of them in Itanhaém and two in Cubatão. Technicians and population were surprised with the fact that the first site at Itanhaém is about 80 Km away from the industry in Cubatão, at Sítio do Coca, Rio Preto road, Km 9. The rest of the sites at this city are located by the same road at Km 6,2 Km 5 and Km 1,8. In Cubatão two different sites besides the industry backyard were found, one at a municipal deactivate dumping domestic waste site, close to Perequê river and the other one close to Cubatão river, inside an ecological park.

During the activities of remote sensorial tracking required and supervised by Cetesb and promoted by the industry in 1993, two other sites were found at Samaritá region: one at Km 65 of the main road and the other at Quarentenário. The quantities of the residues of these last sites seems to be smaller and there is a doubt if they were accidentally disposed during the removing activities from the other sites.

Sítio dos Pilões was inhabited and is very close upstream of the water source for the whole region. This place contains not only residues from Rhodia, but also domestic waste and residues from other industries of Cubatão and many contaminants like heavy metal. Actually, the residues that belong to Rhodia is around 0,5% of the total waste according to the industry. When the residues were found, 120 inhabitants lived in that place with the compacted contaminated soil all around their houses and backyards and even streets.

Some of these residents affirm that part of the organochloride residues disposed at the region were thrown direct to the river so it would not provoke bad smell, like some of the other sites, also dumped or buried near rivers, flooded areas and lagoons. 14

Even though there are many dumping sites assumed by Rhodia all around Baixada Santista and south coast of the State, the principal are located at Samaritá region not only because of the enormous quantity but also because it is a very populated areas. The residues were found by residents that denounced to Cetesb because they were emerging from the soil. There were no control on the scouring powder neither any engineering solution to prevent people and animals from contact with the residues.

The Quarentenário site is one of the more complex sites. There were two well defined dumping areas, one of them over a mangrove, what means that during part of the day it could be covered by the river water during high tide. By the time the first investigations started, before removing the residues, in 1988, there were a few houses very close to the site, one of them had a woman who lived there for more than 17 years. According to her* , a lot of people used to come to her little farm due to the fruits she had and also because the access to go fishing and catching pitu (shrimp) and crab was much easier from her place. Fishing as a hobby or to complement food is still frequent, despite of the chemical waste so close to the river and to the houses.

The most frequent complain of these people was related to the strong smell exhaled by the toxic at the dump site. It caused nausea and headaches, specially on a very hot days after summer rains. All the residents related the worst period for health were when the industry was dumping it and later, when the cleaning activities started, because of the very heavy dust and strong smell could be felt at a very large perimeter from that area. 29

In 1990 the industry stopped removing the soil, put a fence around the big hole it was formed after removal and started to take care of the surveillance of the site. A fence is less than 10 meters apart from the closest house. By that time the excavation area had more than two meters deep and extended for just about ten meters of range. In 1995 a court decision based on a Public Ministry acting plan, ordered the industry to cover the site with canvas and covered with clean soil, starting in 1988 to rebuilt up the scenery with natural species of the region. Also installed monitoring wells, pipes and started pumping out the groundwater to make it go through a charcoal filter and clean it until its pattern is close to water criteria for drinking water fountain supply before withdraw to Mariana river. This treatment begin in October, 1997 for testing the method. Most part of the residues removed from Samaritá soil is stocked at the site 67, where it was constructed the Estação de Espera. All the sites will have the same treatment determined by court decision.

At Km 67 site, located on the right side of the road going south, when the residues were found they were close to a lagoon where the scouring powder drained. The lagoon was entirely drained to Rio Branco without authorization for that and the industry paid a fee for that. This crime against nature elevated the environmental contamination of the river and surround areas. 29

The controlled dump site was built up on a higher part of the land and it was supposed to support around 12.000 tons of residues until final destination. A large area contained two excavated sites had its soil compacted and covered with clay and a polyethylene canvas. The residues were removed from soil and packed in mag-sacs of one ton each. They all received a number and were put inside the dump site using a hoist for that. At the end of the day it should be covered with canvas so there would be no smell and no water would accumulate at the site. 38

The residents from the house right by the site 67 refused to go out of the place until they could have some money from the industry to rebuilt up the house in another place. Only in 1993 the house was demolished and the owners transferred to another place. 29

The resident of the next house used to take care of the place where it is now the controlled site, referred that him and his family had headaches and nausea and itching of their body, what made him talk to the owner of the site to stop allowing the dumping, even though there was an accord with the truck driver to put the residues on that place. After identification of the contaminants this resident and his family moved to the other side of the road to avoid contact with the residues.

At Km 69 site, even though the area occupied by the residues is larger, it is the most protected area to avoid human exposure. There are no houses too close to this site and there is fence around the place, what limits the access to higher contaminated area of the dumping site. The most important worry with this site is the fact that the superficial drain was naturally done passing through an area where it was built the gleba II of Parque das Bandeiras district. The removal of the residues is not still done at this place. 31

The other two sites discovered in 1993 are still intact since they were found. Even though Rhodia affirm 92% of the residues existents are already out of the soil, Cetesb did not released the industry to stop cleaning the soil. Also there is s judicial decision since 12/09/95 that established the necessity of cleaning the soil and superficial and groundwater and control the emissions of the sites, accompanying the contaminated plume of toxic, besides offering water from a safe source to the population of the surrounding area. The costs of this work is something around US$ 9.269.000,00. The industry had appealed to Supreme court but is obligated to enforce the decision until the final court sentence. However, a part of Samaritan’s population still have no safe water supply.

The quantity of the residues to be removed ended up being much higher than it was thought before due to the quality of the soil on this region, with very high humidity and the influences of the tide, what spread out fast the environmental dispersion of the toxic. Even though the very low solubility of HCB, the major compound of the waste is easily carried to the streams on the layers of the soil because of the presence of organic matter, 6 what contribute to elevate the persistence of the pollution on the soil and water. 40

 

3 - Sítio dos Pilões e Perequê

Hexachlorobenzene was found in water, sediments and living organisms; 2.7 of the fish analyzed had higher limits than it is proper for human consumption ( traces to 23.7 ug/Kg for fish muscles and traces to 5.000 ug/Kg for viscera). 14 HCB is also on the river water and sediment, with the samples analyzed varying from 0,2 to 1240 ug/Kg at the sediment and from traces do 0.16 ug/l of the water. 14

It must be said that it is an important worry the fact that this high levels belong to the contamination of a fountain of water supply for many cities from Baixada Santista. Before the impound area by Sabesp, at the right edge of Cubatão river, HCB was found in all the collected samples, with the values varying from 4.75 to 5.50 x 105 ug/l. Besides fecal bacteria and organic heavy metal, HCB was also found at the sediment of the Cubatão river, (hexachlorobenzene 0,008 ug/g, before confluence with Pilões river, and 90,2 ug/g a downstream of the waste site of Pilões and pentachlorophenol 5,5 ug/g and 7,5 ug/g, at the same places. At Pilões river, before Sabesp impound of the water, pentachlorophenol levels were 21,6 ug/g and after ETA-Sabesp, 3,8 ug/g. At the water the levels are much lower but are present in all studied samples, and at the ETA-Sabesp at Pilões river, it was found 21,6 ug/l of pentachlorophenol and 0,89 ug/l of hexachlorobenzene.14

In 1991, Public Ministry and Cetesb found bags and chemicals residues disposed with on land with no protection at all, very close to inhabited houses and with easy access to the place. Some of the residents were living there for more than 20 years. HCB was found at high concentrations, 2,65 g/Kg, and pentachlorophenol, 463 ug/Kg. 14

This type of residues is only found from the production of Rhodia S/A in Cubatão region, so, the link between the findings and the industry responsibility was easy made by Public Ministry and by Cetesb.

To identify routes of human exposure to the organochloride compounds found in Pilões, the City Hall of Cubatão asked analysis of the vegetable and animals used for human consumption at the area. The results are the following:

 

Table 1 - Levels of hexachlorobenze in vegetables and animals specimen of Pilões

SPECIMEN ANALYZED

N.o of the sample

HCB

Chicken

14579

980 ug/kg

Manioc

14582

<0,2 ug/kg

Manioc

14584

9,3 ug/Kg

Inhame

14586

1,5 ug/Kg

Chayote

14588

866,6 ug/Kg

Banana

14590

7,7 ug/Kg

Source: Institute Adolfo Lutz - Proc. 9034/94

These data already show high risk of exposure, especially considering the fact that the residents are at the contaminated area all the time because they live there and plant the crop and create the animals or catch fish from the river. That’s the reason the transfer of the population to another city district was immediately proposed by the State.

 

4 - Samaritá: a public health concern

 

4.1 - Levels of environmental contamination in Samaritá

Cetesb publicized a report on evaluation of organochloride compounds in Samaritá in 1985, where HCB was a major compound of the chemical waste at a level which it represented just about 16% of the total weight; pentachlorophenol, 2,0 to 36,8 mg/g; carbon tetrachloride 6,7 to 842 ug/kg and tetrachloroethilene 295 to 4590 ug/kg. An affluent of Branco river (km 69) had levels between 0,90 to 4,2 ug/l e water from the swamp area (km 67) HCB levels between 0,30 ug/l to 6,2 x 102 ug/l and also, traces of pentachlorophenol. Two wells at Parque das Bandeiras sector had 28 and 42 ug/l de HCB respectively. 9 10 12 15 19

During 1986 year, samples of wells water were analyzed from 25 different areas of the region. Six of them had no level of HCB - nine had higher levels than the ones are recommended by OPAS (1987), for drinking water, 0.01 ug/l.21 The higher levels were 0,15 e 0,19 ug/l. 11 29

In 1987, at Quarentenário site, HCB was detected on the surface of the dump site with values from 342 to 815 mg/kg. At the mangrove area these values were 54,4 to 122 mg/kg; and at the deep soil, 111 and 570 mg/kg.11

There were demarcated 10 different points from the waste site until the last house, what correspond to the point 10, close to Jequié St., at Quarentenário site. The results are the following for water and soil:

 

Table 2 - Levels of HCB on the wells at the region of Quarentenário (m g/l)

Wells

HCB

Pentachlorophenol

CCl4

Tetrachloroethane

1

0,50

0,43

ND

Traces

2

0,75

5,10

16,5

129

3

1,70

1,70

37,0

39,0

4

3,80

2,30

31,5

88,0

5

6,70

1,20

ND

Traces

6

2,20

0,56

ND

Traces

7

0,064

0,55

ND

ND

8

0,35

1,80

ND

ND

9

0,0016

-

ND

ND

10

0,25

Traces

ND

ND

(Source: Cetesb, 1987)6

Table 3 - Levels of HCB no solo da REGION do Quarentenário (m g/kg)

Point

HCB

Pentachlorophenol

1

72,0

2,4

2

40,7

4,7

3

9,8

5,8

4

26,3

2,7

5

10,7

3,8

6

325,0

46,9

7

5,6

2,6

8

1,1

0,52

9

2,04

123,0

10

21,2

7,8

(Source: Cetesb, 1987)6

In the beginning of 1988 Cetesb analyzed some specimen aquatic de Samaritá with the following results:

Table 4 - Levels of HCB in specimen aquatic from Samaritá

SPECIMEN HCB (ug/Kg)
Uca (crab) 2,2
Pitu (shrimp) 2,2
Siri (crab) 7,1
Cará (fish/muscle) 0,6
Cará (innards) 23,6

(Source: Cetesb, 1988)8

Considering all the information obtained, it is supposed that the population in Samaritá could be exposed to the chemical waste at the sites. First, the Quarentenário residents because of the proximity of the very contaminated soil and wells an due to the easy access to the site. Also the Km 69 and Km 67 sites, on the other side of the main road Pe. Manoel da Nóbrega. The streams on the edge of the contaminated sites that lead to Mariana river suffer ebbing tide of the water when there is high tides, passing by the houses of the district; the houses on the side and in front of Km 67 site, because of the proximity is exposed; more remote exposure has the people from Gleba II due to the fact its surface changed during the construction of the district but the surface drainage of the Km 69 site goes direct through the houses; residents of Parque Continental and Conjunto Humaitá, due to the fact that the houses were built up in mangrove landing areas, where the residues may have been carried from Quarentenário, specially considering the flux of the river is slow and may have accumulated contaminated sediments; former residents of any of the districts due to a persistent contact with the residues; the whole population who has the habit of fishing and look for crabs at the region.

 

4.2 - Social, economic and cultural aspects of Samaritá population

A family questionnaire was applied in Samaritá during 1988/89 to a randomized sample of houses through home interview. 29 Besides the general data collected, it was necessary to chose the ones to submit blood sample analysis. The data found about this population are on the following paragraph:

91,6% had income until less than 5 minimum wage, and from these, 51,6% until 3 minimum wage and 13,4% less than one minimum wage. 29

37,62% had no activities out of home, mostly women, 15,15% had no fix job, 12,12% worked with civil constructions, also with no fix job, 10,10% worked for the commerce, 7,07% are metalworker and the rest is dispersed in many other activities; 57,78% work outside Samaritá region; 42,22% of the employment is in Samaritá, 30% in Cubatão, and the rest downtown São Vicente (5,5%) and other cities of Baixada Santista, what confirm the strong influence Cubatão has over the region. 29

190 residents informed their precedence, 84 (44,21%) came from Cubatão. 50,3% were born in different States from the northeast part of Brazil, 15,9% came from other States from Southeast, 10,4% were born in Santos and 6,9% in Cubatão. Only 1,7% were born in Samaritá, what confirm the great influence of migration from northeast part of Brazil to the region.

Asked about health problems, 43,40% answered the question; most of them complained about circulatory problems (15,53%), no defined complains, like headaches, dizziness, weakness (11,65%) and respiratory diseases (10,67%). The link between complains and the exposure could not be made on this research but it is surprising that in a morbidity study done before at Gleba II, by Instituto de Saúde, SP, most part of the residents complained about osteoarticular problems. 29

Only 20,39% from the 201 that answered the question affirm to frequent mangrove areas and the rivers to go fishing, but what can be seen on weekends show a different information. Many people go after the water for fun or supply of food.

 

4.3 - Levels of HCB at Samarita population

In 1989 10 samples of human milk were collected. One of them was lost during transport until Adolfo Lutz Institute, SP, where they were analyzed. All the women lived in Samarita for more than 12 months and were breast feeding between 2 and 24 weeks. Time of residence was between one and 15 years and age between 17 and 30 years old. Levels of HCB were 0,07 ug/Kg of fat until 29,03 ug/Kg, and was detected in all samples.29

Among the three women who had the higher levels (1,32 ug/Kg, 8,67 ug/Kg e 29,03 ug/Kg), all used to have food from the region and lived between 300 and 600 meters of distance from the waste sites and lived more than three years at the same place. Two of them, who had the higher levels, used water from wells of the region (8,67 ug/Kg e 29,03 ug/Kg). Other organochloride were also found including hexachlorociclohexane - HCH was also found. 29

To help testing methodology ten blood samples from residents with age more than 15 years old, 5 men and 5 women of Samaritá and ten (5/5) from Itanhaém were collected to analyze organochloride residues on the blood. The analysis was made by Institute Adolfo Lutz - IAL/São Paulo. All samples from Samaritá had some level of HCB and no one from Itanhaém had it, what showed HCB could indicate the contact with the residues.

The results from the tests on blood are the following:

 

4.3.1 - Levels of HCB on blood of Samarita population **

234 persons, 102 man (43,59%) e 132 women (56,41%), submitted to the exam between December/88 to march/89, distributed through the following sectors: (Figure 3 - Samaritá map and the districts divided by studied sectors).

Table 5 - Distribution of population according to sex

SEX

SECTOR

Male

Female

Total

A

5

9

14

B

32

36

68

C

39

59

98

D

9

8

17

E

7

6

13

F

10

14

24

TOTAL

102

132

234

Chi-square tests shows no differences for sex among the six sectors:

Chi-square = 2,456 G.L. = 5 Prob. = 0,7830

For age variance analysis were applied and also no different distribution among sector were found:

Table 6 - Distribution of the population according to age

SECTOR n MEAN
A 14 30,786
B 68 36,638
C 98 35,333
D 17 31,412
E 13 42,923
F 24 33,708
TOTAL\MEAN OF TOTAL 234 35,416

 

SOURCE VARIATION

GL

å SQUARES

SQUARE MEAN

F OBSERVED

p

Between sectors

5

1478,986

295,797

1,530

0,1813

Residue

229

43883,632

193,920

   

TOTAL

234

45362,618

     

HCB (ug/l) mean levels of the sectors were compared and there is a significant difference between sector A and the other sectors:

Table 7 - Levels of HCB at the studied population in Samaritá m g/l)

SECTORS

n

MEAN

A

14

4,095

B

68

0,414

C

98

0,378

D

17

0,341

E

13

0,397

F

24

0,363

TOTAL

234

0,607

SOURCE VARIATION

GL

SOMA DOS SQUARES

SQUARE MEAN

F OBSERVED

p

Between sectors

5

181,248

36,250

22,915

<0,001

Residue

229

362,499

1,517

   

TOTAL

234

543,509

     

 

Taking out Sector A to see if there differences among the others, the differences started to be of no statistic significance:

SOURCE VARIATION

GL

SOMA DOS SQUARES

SQUARE MEAN

F OBSERVED

P

Between sectors

4

0,107

0,027

0,592

0,6684

Residue

216

9,783

0,045

   

TOTAL

220

9,890

     

The use of water from the wells of the area shows possible routes of exposure. The results shows statistic differences among the sectors (p<0.001)

Table 8 - Frequency of the use of water from wells in Samaritá

SECTORS

YES

NO

TOTAL

A

14

0

14

B

51

17

68

C

40

58

98

D

2

15

17

E

1

12

13

F

18

6

24

TOTAL

126

108

234

Chi- square = 58,517, G.L. = 5, Prob. <0,001

The habit to eat fish, crab, shrimp, chicken, pig and vegetables produced or catch in Samaritá can also show routes of exposure. The differences are also statistically significant (p<0.05):

Table 9 - Frequency of use of food produced in Samaritá region

SECTORS

YES

NO

TOTAL

A

8

3

11

B

32

34

66

C

42

56

98

D

4

13

17

E

9

4

13

F

7

17

24

TOTAL

102

127

229

Chi-square = 14,384 GL = 5 Prob. = 0,0132

Time of residence was compared among sectors and an important difference between sector E appears to be significant, for it is the most antique sector of the region:

Table 10 -Time of residence in Samaritá

SECTORS

n

MEAN OBSERVED

A

11

6,182

B

68

8,956

C

95

8,768

D

17

2,000

E

12

19,000

F

22

6,955

TOTAL

225

8,556

SOURCE VARIATION

GL

å SQUARES

SQUARE MEAN

F OBSERVED

P

Between sectors

5

2173,192

434,638

13,260

<0,001

Residue

219

7178,364

32,778

   

TOTAL

224

9351,556

     

Taking out Sector D (new sector) and E (the former), which had respectively, 2,0 and 19,0 years of residence, differences disappeared:

SOURCE VARIATION

GL

SOMA DOS SQUARES

SQUARE MEAN

F OBSERVED

P

Between sectors

3

132,590

44,197

1,764

0,154

Residue

192

4810,364

25,054

   

TOTAL

195

4942,954

     

 

4.3.1 - Levels of HCB in human milk*

In 1994 a controlled cross-sectional study was made 39, which main objectives were suggesting biomarker for health monitoring of the exposed population in Samaritá. 40 samples of human milk and blood serum, 23 from Samaritá and 17 from control population, were collected and analyzed. There were no differences between the two populations according to age, sex and number of pregnancies, abortions and time of breast feeding. HCB was not found in any of the blood samples, nevertheless it was found in 20 of the human milk samples, 14 (60,9%) in Samaritá and 6 (35%) from control population. Total HCH (a , b , g ) was found in 90,0 % and DDT (p-p’DDE, p-p’DDD, o-p’ e p-p’ DDT) in 100% of the human milk samples. Also DDT was in 42,5 % of the serum blood samples.

There were no significant differences between studied and control population, even though Samaritá’s mean values are higher than control population. Time of exposition may have influenced the results. HCB levels in human milk may be better used for monitoring exposed population than blood serum because organochloride residues have higher levels and were more often detected in milk samples.

Table 11 - Levels of organochloride residues in human milk

at the studied population - ng/g (ppb)

TOTAL n = 40

 

n=+

%

(Xmin Xmax )

MEAN

SD

Median

HCB

20

50

(0,22; 1,04)

0,24

0,29

0,22

HCH

36

90

(0,66; 25)

5,91

7,10

2,67

DDT - total

40

100

(1,20;377,07)

60,99

98,66

22,48

Heptachlor

33

82,5

(0,42;36,22)

2,44

5,80

1,06

SAMARITÁ n = 23

  n=+

%

(Xmín Xmáx )

MEAN

SD

Median

HCB

14

60,8

(0,25; 1,04)

0,29

0,29

0,25

HCH total

20

86,95

(0,66; 22,86)

5,6

6,95

2,79

DDT - total

23

100

(1,20;348,72)

40,62

78,33

15,94

Heptachlor

19

82,6

(0,42;36,22)

3,03

7,47

1,055

CONTROL n = 17

 

n=+

%

(Xmín Xmáx )

MEAN

SD

Median

HCB

6

35

(0,22; 0,97)

0,17

0,28

1

HCH total

16

94

(0,66; 25)

6,33

7,50

2,33

DDT - total

17

100

(4,12;377,67)

88,55

117,83

34,68

Heptachlor

14

82,35

(0,52;8,20)

1,65

2,01

1,15

Table 12 - Levels of organochloride residues at the studied population

TOTAL n = 40

 

n=+

%

(Xmín Xmáx )

MEAN

SD

Median

HCB

ND*

         
HCH total

ND

         
DDT - total

17

42,5

(0,08; 2,77)

0,23

0,58

0,00

Heptachlor

ND

         

ND 8= No detected

SAMARITÁ n = 23

 

n=+

%

(Xmín Xmáx )

MEAN

SD

Median

HCB

ND

         
HCH total

ND

         
DDT - total

9

39,13

(0,08; 1,67)

0,13

0,35

0,00

Heptachlor ND          

 

CONTROL n = 17

 

n=+

%

(Xmín Xmáx )

MEAN

SD

Median

HCB

ND

         
HCH total

ND

         
DDT - total

8

47,5

(0,09; 2,67)

0,37

0,78

0,00

Heptachlor

ND

         

 

Table 13 - Relative risk to present HCB detected levels in

human milk for residents of Samaritá

 

 

HCB +

HCB -

Total

Samaritá

14

9

23

Control

6

11

17

Total

20

20

40

OR = 2,85 (0,65<OR<13,01) RR = 1,72 (0,84<RR<3,55)

 

Chi square p

No correction 2,56 0,1097689

Mantel-Haenszel 2,49 0,1143095

Yates correction 1,64 0,2007611

 

5 - Chemical Unit of Cubatão - UQC, Rhodia S/A

 

5.1 - Levels of environmental contamination

In 1993 Cetesb collected samples from the soil and ashes from the incinerator and from many other points at the chemical plant of Rhodia S/A attending a formal resolution of the Public Ministry. The results were organized by Augusto4 as following:

Table 14 - Results of sample analysis of the environment at the UQC

POINT HCB (mg/Kg) PENTACHLOROPHENOL (mg/Kg)
well excavated 374,0 1,83
stock-room - Galpão II 604,0 7,94
box of mixture - 1,90
ashes landing 65,4 8,30
stock-room - Galpão II 767,0 3,25
ashes from incinerator 0,39 2,67

Source: Ministério Público-SP 199323

It was a surprise for Public Ministry to find hidden disposal of waste inside the area of the industry without any protection for the scouring powder and also to find out high levels of organochloride compounds at the incinerator ashes. These data plus the health risk assessment of the workers gave the arguments to ask for a court decision to close the industry until control the situation.

According to CSD-Geoklok, 1996 Vol. 1 - "UQC - Diagnóstico e Projetos de Recuperação Ambiental",21 there are 3.300 Kg of organochloride dissolved in underground water and 660 Kg released and not reacted. At Perequê river the levels of organochloride get higher after passing the industry, probably due to the release from contaminated surface and ground water. At the chemical plant there are higher levels of heavy organochloride compounds like HCB and pentachlorobenzene, specially on the drainage area close to the stock -rooms. 21

In 1998, complementing evaluation, CSD-Geoklok affirm that the greater plume have a well defined source on Carbon tetrachloride plant and at the two stock -rooms, I and II. This is also valid for the deep underwater (crystal-clear water aquifer) which contamination appears to be associated to vertical migration of upper layers of groundwater (sediment aquifer) and from the contaminated surface soil and water , well identified in 199631. (Figure 4 - Isoconcentration of organochlorine compounds light, heavy and total, at the main underground water, Oct./96)*

 

5.2 - Determining occupational exposure

According to Rhodia S/A, 74 workers were submitted to blood analysis for organochloride residues during the process of closing the factory, and had HCB levels between 0,1 to 16 ug/dl. 29

AUGUSTO (1995)4 studied HCB levels in blood from four different groups of exposure to the residues of the factory, analyzed from 1992 to 1994. The groups are: 179 workers of the UQC - Rhodia ( mean = 3,0 ug/dl; min. = 0,1 ug/dl; max. = 16 ug/ SD = 3,1 ug/dl), 10 workers from another company contracted by Rhodia (mean = 0,2 ug/dl; min. = 0,03 ug/dl; max. = 1,3 ug/dl; SD = 0,1 ug/dl), 18 persons of families of four workers of the UQC (mean = 0,05 ug/dl; min. = 0,0; max. = 0,2 ug/dl; SD = 0,06 ug/dl) and 36 workers from another industries of Cubatão (mean = 0,0008 ug/dl; min. = 0,0; max. = 0,03 ug/dl; SD = 0,0009 ug/dl). Comparing the groups through Kruskal-Wallis test (KW) there are significant differences among them (p<0,000001).4

From the 179 workers of the UQC, 85 went through clinical and toxicological trial, and Augusto4 found positive correlation between time of work at the chemical plant and serum level of HCB. The workers who had direct contact with the production had the higher levels of HCB and actually it was possible to see a graduation of risk inside the factory. 4

To evaluate the breaking of chromosomes, clastogenic effects - the interference on the mitotic division, Augusto4 submitted 41 workers of the UQC and 28 controls to tests of micronucleus counting, and found a significant difference among the two groups that are not related to time of exposure, age and HCB blood level. The study had control about smoking habit. Exposed group had a mean values of 1,97% ( 0,6% to 4,8% ) and control group, 0,25% (0,0% to 2,2%), and this difference is statistic significant. 4

Table 15 - Distribution of 41 exposed to organochloride and 28 controls,

according to the frequency of micronucleus, using the cut value 0,7%

(mean plus standard deviation of the controls)*

 

MICRONUCLEUS

GROUP

< 0,7

= 0,7

EXPOSED

5

36

NO EXPOSED

24

4

Fisher test p=6,61 x 10-10 4

A clinical trial was also made among these group of 85 workers by Augusto 4 and the distribution is alike what is found in literature of chronic exposed population to organochloride. They are neuro-psychologic (n=75, 76,4%) and among them, the most frequent were headache (n=45, 69,2%), weakness (n=30, 46,1%), irritability (n=26, 40%) and difficult to memorize things (n=18, 27,7%). 18 of them had liver problems, and from these, 4 had liver steatosis, 2 chronic hepatitis and 8 had high enzymatic activity (TGO and TGP), among some others. Osteomuscular complains appeared in 38 (44,7%), gastrointestinal disorders in 36%, dermatology problems in 33 (38,8%), immunology disorders in 24 (28,2%), respiratory problems in 8 (9,4%), cardiovascular and genito-urinary complains 6 (7,0%) and others, 11(12,9%).4

Must be investigated the basic cause of death of the workers of the UQC. Four workers that operate the incinerator on the age of 29, 32, 36 e 52 years old died between 1992 and 1994 and at least two of them ( 32 and 36 years old), with a very similar clinical symptoms, with a fast emphasize slimming deterioration of vital functions, compatible with acute immunology distress and negative tests for Aids. Until now there are no mortality and lethality studies of the chemical plant workers.

 

6 - Nowadays situation of "case Rhodia"

According to CSD-Geoklock studies, there are still 238,6 tons of residues impregnated to the soil in Samaritá region; a water contaminated plume has around 9,4 hectares, and a volume of 142.000 m3 and a total of 104,2 Kg of organochloride. 31

Also, it is expected an annual income of volatilization of the residues around 633,9 g/year at Km 67; 3.831,5 g/year at Km 69; and 15,3 g/year at Quarentenário and 1.438,0 g/year no PI-05 sites. 31

A technical plan to control emissions and the enlargement of the plume of residues, as well as "in situ" treatment and hydraulic contention must be done in all sites. Underground water will be pumped to treatment system that ends with 4 charcoal filters; the objective of this treatment is to obtain legal water patterns for drinking water source. The system is already installed at the Quarentenario site and is being constructed and testing in some of the others, including the UQC - Cubatão. The environmental agency did no analyze the whole project proposed by the industry and accepted by Public Ministry but is monitoring the results.

Bio-remmediation with fungus studies are being developed by State University of São Paulo - UNESP 40, with an agreement University-industry, financed in great part by the industry Rhodia S/A. Even though the first results are encouraging, especially related to the international experience, the project is still an experiment and is finally preparing the beginning of the field tests. 40

The workers are being submitted to clinical analysis to enforce the agreement among the parts, under supervision of technicians designated by the industry, the trade union organization and from Public Ministry. Until now there is no clear evidence that the whole story is getting to the end, even though the first expire date for definition ends up this year, 1998. The future of these workers is still unknown.

The surrounding population of the sites in Samaritá is still growing and great part of them still have no safe water supply. Some of the benefits of urbanization like asphalt and public illumination are already available to the districts but water and sewer services supply does not seems to have a close solution. There is no health diagnosis neither any monitoring plan to identify exposure and health problems. The health units of the region are precarious and have no specialized health workers and equipment that are necessary for this approach.

 

7 - Final considerations and recommendations

Solid industrial residues are a concern of the whole planet even to undeveloped nations because if they do not produce them in large amount, they have more difficulty to repair the problems.

The development model adopted in Brazil produces areas of extreme contrast, with industrial development living close together with extreme poverty, like it happens in Cubatão. Many workers migrated from other parts of the country attracted by offering of jobs. There is no place for them in the cities, so they go living in difficult places like mangrove areas or slums, close to polluted industries and suffering the impact of total lacking of infra-structure.

The extreme poverty perpetuate by low qualification jobs makes the familiarity of predictable infectious disease with pollution from industrialized areas.

Also, the technology adopted in the country is very often scrap metal at developed countries and brings a dirty production what makes waste of natural resources and have high pollution capability. The lack of a careful plan of industrial areas makes all the problems to become acute and multiply them, making a very dangerous mixture that often ends up with serious environmental problems like Cubatão.

Yet, the lack of a policy to make less residues production made it easier the appearing of problems of difficult and onerous solutions of limit situations like this studied case. The omission of the Government authorities has a difficult established price like when there is contamination of water fountains supply or degradation of marine environment, for example.

On the other hand, Government decisions took too long and rarely had in consideration all parts involved in the process, what let protection to the exposed population depending almost exclusively on the initiative of the industry. Also, different governmental organizations like Secretary of Health and Environment Agency did not work on a plan for acting together on this case. May be that is the reason why a lot of money was spent looking for new sites while nothing was made to control the contaminated plume on soil and groundwater, neither any strategy to avoid public exposure to the chemicals and that should be a priority. The surrounding area of Quarentenario, for example, had a explosive increase of population with no planning at all, making bigger the problem.

HCB is a good biomarker for exposure to the residues of the UQC - Cubatão. Although other organochloride compounds appears in all analyzed samples at high levels for international patterns, what is a matter of concern itself, HCB is not usually found in Brazil.

Human milk is much more sensitive to identify environment exposure to organochloride compounds than blood samples as shown in this case study.

The control and continence of the chemical waste sites are not enough to avoid human exposure until now.

Monitoring of HCB levels at the exposed population may give some parameters to evaluate exposure to the chemicals at the waste sites but it cannot be the only biomarker of exposure. Finding clinical biomarkers for this population can be an important objective of the local health service.

There are significant differences among studied regions and populations due to the grade of exposure related to the level of HCB on the analyzed samples. The differences are of statistic significance specially among the workers of the chemical industry. More research must be made to better understand routes of exposition to these chemicals specially on the surrounding area of the waste sites.

But residues of HCB in blood or human milk cannot be considered the only effect of the frequent contact with the hazardous waste. To publicize the results without understanding the context may generate a false idea that it means disease and also, that there is no risk if it is not found at detected levels.

More research is still necessary to make health diagnosis of the exposed population. But it is also necessary to offer good health assistance and monitoring to make registry of morbidity, mortality, abortions, premature newborn, teratogenicity etc. Any inference about health evaluation without this type of information will always be missing information and can mislead results. A well organized health local unit with capability to solve most part of health problems, having equipment and well formed health workers will be able to have the confidence of the population and notify any of these data and the capacity to solve problems will bring all the information that is missing nowadays.

It is urgent to look for a solution for the enormous quantity of residues at Samarita landfill. The incineration. Incineration seems to be a very conflicting solution due to health and environmental risks and also due to the impossibility of control and continuous monitoring of dioxin in Brazil. The incinerator built by Rhodia S/A in Cubatão is still closed together with the chemical plant by judicial decision. Besides that, it is located in a extremely contaminated site as it was shown on this paper, representing, for this reason, a great environmental risk to add more pollutants to the environment.

It is necessary to implement risk communication to the workers and to the population living on the surrounding area of the dump sites. Also it is necessary to have free monitoring data accessible to technicians and general public. A periodic publication of the data for involved communities would generate less misunderstanding and probably better and faster solutions.

This case is an example to show negligence, fault or fraud of a chemical industry can result in high cost to the environment, to health care services, and also lead to an expensive and not always effective process of control and remediation. This high cost can yet determinate destruction or paralysis of resources and productive capabilities of the industry and sometimes of the whole region.

Ideal solutions do not exist, so all resolutions must be negotiated with al involved parts of the problem in a transparent process. Information and decision must have the control of organized society. That is the only way to assure emissions are under control and to acquire security to affirm there is no reason for great alarm.

Monitoring the involved population can lead to more effective control of the emissions and a risk evaluation based on specific criteria. Since there is no way to deactivate this environmental time bomb, at least it is necessary to exactly know the risk to attempt minimize its effects. Even though that is not the ideal anyone wanted, that is the best inheritance we can delegate to further generations.

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