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Report on air quality for aldehydes, benzene, PM10 and ozone in BrazilReport on air quality for aldehydes, benzene, PM10 and ozone in BrazilFormatted: Font: 20 pt

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Photo of Rio de Janeiro smog from space.

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Rolands Jaunzems (2040973) Reineke Klein Entink December 2010

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Table of ContentsIntroduction................................ ................................ ................................ ................................ ... 43 Contaminants and concentrations ................................ ................................ ................................ ... 54 Air pollutants ................................ ................................ ................................ ................................ . 65 3.1 3.2 3.3 3.4 Atmospheric aldehyde ................................ ................................ ................................ ............ 65 Benzene ................................ ................................ ................................ ................................ . 98 PM10................................ ................................ ................................ ................................ ... 1211 Ozone................................ ................................ ................................ ................................ . 1312

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4 5 6

Air quality policies ................................ ................................ ................................ ..................... 1513 Conclusions and recommendations ................................ ................................ ............................. 1715 Bibliography ................................ ................................ ................................ ............................... 1716Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar Formatted: Default Paragraph Font, Font: (Default) Calibri, 11 pt, Not Bold, English (U.S.), Check spelling and grammar

Introduction ................................ ................................ ................................ ................................ ............ 3 Contaminants and concentrations ................................ ................................ ................................ ........... 4 Air pollutants ................................ ................................ ................................ ................................ ........... 5 Atmospheric aldehyde ................................ ................................ ................................ ......................... 5 Benzene................................ ................................ ................................ ................................ ............... 8 PM10 ................................ ................................ ................................ ................................ ................. 10 Ozone ................................ ................................ ................................ ................................ ................ 11 Air quality policies ................................ ................................ ................................ ................................ . 12 Conclusions and recomendations ................................ ................................ ................................ .......... 14 Bibliography ................................ ................................ ................................ ................................ .......... 14

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21 IntroductionAir pollution is described as the presents of chemicals, physical agents, or biological materials that cause harm or discomfort to people or other living beings, or cause damage to the natural environment or built environment, into the atmosphere. Worldwide different household combustion applications, motored vehicles (with combustion engine), industrial facilities and wild fires are major sources of air pollution. Pollutants like nitrogen dioxide, sulfur dioxide and carbon monoxide are major public health concern include particulate matter. Outdoor air pollution often is cause of respiratory and other diseases, which can be fatal. Humans probably first met polluted air at their poor ventilated caves from fireplaces. Since that time we have gone polluting air much more over the world. Until recently, environmental pollution problems were more local and not so big because of Earths own ability to absorb minor amounts of pollution. Development of production of goods, introduction of motorized vehicles and urbanization with explosion of population is factors that contribute towards the growing air pollution problems. At this time it is necessary that we look for methods to clean up the air. The primary air pollutants found in most urban areas around the world are carbon oxides, nitrogen oxides, sulfur oxides, hydrocarbons, and particulate matter. These pollutants are distributed throughout the world's atmosphere in some places concentrations high enough to cause serious health problems. Serious health problems can occur quickly when air pollutants are concentrated, such as when massive injections of sulfur dioxide and suspended particulate matter are emitted from volcanoes. Same as many big countries all over the world Brazil also must deal with poor air quality. Brazil officially the Federative Republic of Brazil is the largest country in South America. It is the world's fifth largest country, both by geographical area and by population. [1][2]Air pollution in Brazil is mainly due to rapid urbanization in several cities that lacked the infrastructure to support rapid population growth. A recent World Bank study ranked the Brazilian cities Sao Paulo, Rio de Janeiro, Belo Horizonte and Curitiba as the four most polluted cities in the country. Sao Paulo, Latin America's second largest city (behind Mexico City), experiences the same problems that many other large cities face when the population grows faster than the infrastructure to support it. Traffic congestion and pollution are two major problems affecting Sao Paulo. In 1989, 50% of city smog resulted from factories and 50% from motor vehicle emissions. In 1999, the percentages were 10% and 90% respectively. [4] Acknowledging possible air pollution problems in South America this report is made as a part of study project Environment and Health at Avans University of Applied Science. In this report closer look on South Americas biggest country Brazils air pollution will be described. First chapter describes contaminants and concentrations found in Brazil. Main air pollutants like atmospheric aldehide, benzene, ozone and PM 10with their influence on health and environment will beare described in chapters 3.1 to 3.4 in chapter as well as recent pollutant measurement data described and compared to European Union standards. Review of air policies in Brazil is4

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placed in chapter 4. Conclusios and recommendations are laid out in chapter 5 after which bibliography is summarized. Name content of all chapters and preferably also the chapter numbers Good introduction!

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32 Contaminants and concentrations chapter numberAir in big cities of Brazil is mostly polluted by motored vehicles. Population and urbanization has kicked hard to air quality. Infrastructure has not been able to catch up with growth of population. Public transportation was organized not the best way. That all was leading to bad air quality. Debate of national level raised and in 1970s first air quality policies started to develop. Sao Paulo's pollution levels are fuelled by poor infrastructure design, gasoline prices that are among the lowest in the world and inefficient automobiles. Government initiatives to improve environmental conditions in Sao Paulo include plans for an orbital motorway (expected to reduce city traffic by 20%), additional metro lines, and improvements to the rail system by 2002. [5] Part of solution was also substituting the fossil fuel use for light motored vehicles to bio fuel or ethanol. Brazil is on a path to independence from foreign oil, by developing its own oil reserves and by investing heavily in renewable energy from ethanol. About 40% of the fuel Brazilians use in their vehicles is ethanol.[6] Public thought and displayed by media thought was that this portion of bio fuel use in transportation in Brazil must be helping a lot in improving air quality. But there was no certainty what the actual situation of air quality in Brazil is. Boggled by this question further investigation was advised and some researches were started. These researches like Niven[7] on Environmental impacts and sustainability of ethanol in gasoline gathers data about air contaminants in multiple places in different cities of Brazil. Most common light vehicle emitted pollutants in Brazil are COx, HC, NOx,aldehydesand benzene. Martins et al.[8]have reported the results of extensive measurements of CO, CO2, NOx, sulfur dioxide (SO2) and individual HC and carbonyl compounds both inside and outside of tunnels in Sao Paulo, Brazil. Samples were collected in the Janio Quadros Tunnel during late March 2004 and in the Maria Maluf Tunnel in early May 2004. On average 95% of the vehicles passing through the Janio Quadros Tunnel use either gasohol or hydrous ethanol, with the remaining vehicles being light duty vehicles burning diesel fuel. On average 13% of the vehicles using the Maria Maluf Tunnel are heavy dut y diesel fueled, with the remaining fueled by gasohol or hydrous ethanol. These data were used to determine emission factors for various compounds from the vehicle fleet. Vehicle related emission measurements at Maria Maluf Tunnel [6] * CO g/km NOx g/km Light duty vehicles 2.3 14.6 0.3 1.6 Heavy duty vehicles 4.7 20.6 9.8 22.3 Organic compound \ Place Maria Maluf Tunnel CH2O 35.1 48.4 mg/km5

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CH3CHO Benzene Toluene Ethylbenzene m,p-xylene o-xylene

29.1 45.7 mg/km 72.0 78.3 mg/km 134.5 135.4 mg/km 31.1 33.0 mg/km 62.0 62.8 mg/km 39.8 44.4 mg/km

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For the light duty vehicles the emissions factors for CO and NOx were found to be 14.6 - 2.3 g km-1 and 1.6 - 0.3 g km-1 respectively, while for the heavy duty vehicles these emissions factors were found to be 20.6 - 4.7 g km -1 and 22.3 - 9.8 g km-1 respectively. The average emission factors for the following organic compounds in the Maria Maluf Tunnel were: CH2O 48.4 - 35.1 mg km-1; CH3CHO 45.7 - 29.1 mg km-1; benzene 78.3 - 72.0 mg km-1; toluene 134.5 - 135.4 mg km-1; ethylbenzene 31.1 - 33.0 mg km-1; m,p-xylene 62.0 - 62.8 mg km-1; and o-xylene 44.4 39.8 mg km -1. *The average molar CH2O/CH3CHO ratio in emissions from these vehicles is 1.5.[8] Data in yellow -> better make a table out of it (not very easy to read) Industry is also one of the major polluters of air in Brazil. Burning of biomass and fossil fuels (coal and petroleum by-products) also give rise to SO2, CO2, emit PM10. SO2 chemical compound is also a result from sulfur oxidation occurring during the fusion of cooper, zinc and lead sulfides in the metallurgic plants.

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43 Air pollutantsAir pollutants occur both outdoors and indoors and can be man-made or nature-made. Outdoor air pollution, also called ambient air pollution, occurs in both urban and rural areas. Different mix of air pollutants may be found in the country sides to that found in cities. It is especially interesting to look at Brazils air conditions when we know it is using ethanol and mix ethanol into gasoline for car fuel. Ethanol fuel fulfills almost 20% of all fuel consumption needs so pollution created by traffic could make a different mixture of pollutants in the air what could cause all kind of environment and health hazards.

4.13.1 Atmospheric aldehyde Any of a class of organic compounds that contain the carbonyl group, and in which the carbonyl group is bonded to at least one hydrogen; the general formula for an aldehyde is RCHO, where R is hydrogen or an alkyl or aryl group. Aldehydes are formed by partial oxidation of primary alcohols and form carboxylic acids when they are further oxidized. The common name for an aldehyde is often derived from the name of the acid it forms; the IUPAC name is usually derived from the name of the alcohol from which it is formed. Low molecular weight aldehydes, e.g., formaldehyde and acetaldehyde , have sharp, unpleasant odorsodours; higher molecular weight aldehydes, e.g., benzaldehyde and furfural , have pleasant, often flowery, odorsodours and are found in the essential oils of certain plants. Aldehydes are used for the manufacture of synthetic resins, e.g., bakelite, and for making dyestuffs, flavorings, perfumes, and other chemicals.[19] Some are used as preservatives and disinfectants.Concentrations

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The results of early measurements of total aldehyde concentrations in Sao Paulo have been reported.[9] These measurements of total aldehydes were made using the 3-methyl-2benzothiazolinone hydrochloride (MBTH) method. This method measures total aldehydes, not individual compounds. The concentration results are presented as CH2O. Long-term monitoring was reported for four sites in Sao Paulo. This long-term monitoring consisted of 24 h sampling periods on weekdays (MondayFriday) at each of the four sites from July 1980 to June 1981. The average concentrations of the total aldehydes reported at each of these sites over the year are shown in the table below.Table1 Month/year Jul. 1980 Jun.1981 Jul. 1980 Jun.1981 Jul. 1980 Jun.1981 Jul. 1980 Jun.1981 Location Praca do Correio Parque DomPedro Mooca Congonhas CH2O/ppb Total aldehydes Total aldehydes Total aldehydes Total aldehydes CH3CHO/pp b 42 20 15 27 CH2O/CH 3CH Oratio Number ofsamples ~260 ~260 ~260 ~260 Samplepe riod/h 24 24 24 24Formatted: No underline, Font color: Auto, Subscript Formatted: No underline, Font color: Auto, Subscript Formatted: No underline, Font color: Auto, Subscript Formatted: No underline, Font color: Auto, Subscript

More recent measurements have been taken in Sa ~o Paulo. More than 30 different measurement researches were done during last years with more than 1300 samples of air measured.Table2 Month/year Mar.Apr. 1990 Aug. 1990 1993 Oct. 96Jan. 97 Jul.Sep. 1997 Jul.Oct. 2006 Jun.Jul. 1988 Oct. 96Jan. 97 Feb. 1998 Nov. 2000 Aug. 2002 Feb. 2007 Aug. 2001 Oct. 2001 Location Cerqueira C_esar Cerqueira C_esar Cerqueira C_esar Cerqueira C_esar Cerqueira C_esar Cerqueira C_esar Univ. Sao Paulo Univ. Sao Paulo Univ. Sao Paulo Univ. Sao Paulo Univ. Sao Paulo Univ. Sao Paulo Janio Quadros Tunnel Maria Maluf CH2O/ ppb 15.5 21.8 7.6 5.4 7.0 5.7 8.8 1.3 5 4.2 4.0 13.5 2431 2839 CH3CHO/p pb 24.3 27.3 10.6 7.5 11.7 5.6 7.6 2.8 5.4 3435 2532 CH2O/CH3CHO ratio 0.6 0.8 0.7 0.7 0.6 1.0 2.5 0.5 0.9 0.9 1.0 Number of samples 23 6 180 132 155 141 8 60 11 18 30 5 Sample period/h 2 24 1 2 1 2 2 2Formatted: No underline, Font color: Auto, Subscript Formatted: No underline, Font color: Auto, Subscript Formatted: No underline, Font color: Auto, Subscript Formatted: No underline, Font color: Auto, Subscript

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Oct. 2001 Mar.Apr. 2004

Tunnel Ambient-Maria Maluf Fourteen locations

1.046 18.1

4.251 15.4

1.4 1.2

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In table 2 you can see shortened summary of ambient CH2O, CH3CHO and CH2O/CH3CHO ratio data in Sao Paulo, Brazil. The CETESB[10] conducted an aldehyde measurement campaign between July and October 2006 at the Cerqueira Cesar site in Sao Paulo. The average concentrations reported for the 141 samples of 2 h duration were 5.7 ppb for CH 2O and 5.6 ppb for CH3CHO. These concentrations are somewhat lower than those reported at the same site during a similar time period in 1997, which found average concentrations of 7.0 ppb and 11.7 ppb, for CH 2O and CH3CHO respectively. Similar tests for aldahydes were done in Rio de Janeiro. Table 3Month/year Jan. 1987 Jan. 1993 Apr. 2002 Feb. 2003 Nov. 2005 Aug. 2006 Nov. 2005 Aug. 2006 2006 2008 Location Reboucas Tunnel Six locations Tijuca District Bus, airconditioned Bus station Eight location Alto Floresta da Tijuca CH2O/ppb 154 9.7 151 39 118 10.1 13.1 CH3CHO/ppb 307 28 30 32 89 11.1 4.5 CH2O/CH3CHO ratio 0.5 0.5 4.9 1.6 1.4 0.9 2.9 Number of samples 1 6 86 6 5 8 34 Sample period/h 6-8 2 1 2

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Summary of ambient CH2 O, CH3 CHO and CH2 O/CH3 CHO ratio data in Rio de Janeiro, Brazil

Grosjean et al.[11] present results of carbonyl sampling studies during the late 1980s using DNPH coated cartridges conducted at three sites in Sao Paulo, two sites in Rio de Janeiro, and one site in Salvador. The results of these measurements made in the different areas of Brazil are presented in Table 1 and 2 for Sao Paulo, Table 3 for Rio de Janeiro. The sampling was done during the winter and early spring to minimize the contribution of photochemistry, and one of the sites in Rio de Janeiro was in a tunnel which would be more representative of on-road vehicle emissions. It was concluded [11] that CH2O concentrations measured in Brazil are as high as those measured elsewhere in the world, but not substantially higher, while CH3CHO concentrations were substantially higher, and the CH2O/CH3CHO ratio was consistently lower than that measured elsewhere. Furthermore, the tunnel data clearly show very high levels of vehicle emissions of CH3CHO compared to CH2O. The very high ambient concentrations of CH3CHO are likely due to the large scale use of ethanol as a vehicle fuel. Comparing aldehyde pollution to world other cities Brazil results look similar but in some cases measurements are much higher. In following table will display measured aldehyde presence in other parts of world.8

Table 4 Aldehyde measurements around the world [12] title (add source as well)Month/year Summer (August) 1994 MarchMay 1993 November 1996 Location Milan, Italy Mexico city, Mexico Downtown Savannah, GA, USA Rio de Janeiro, Brazil Average aldehyde concentration ( g/m3)* Formaldehyde CH2O Acetaldehyde CH3CHO 8.9 13.7 43.5 2.0 33.8 2.3 10.43 27.09

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May to November 10.84 2000 June to October Beijing, China 29.34 2008 Concentrations of aldehydes in ambient air in different cities.*ug/m3 = (ppb x Mw x Tsd x Pm)/(22.4136 x Tm x Psd) ppb = concentration Mw = molecular weight Tsd = standard temperature Pm = measured presure Tm = measured temperature Psd = standard pressure

Impact of pollutant

Impact of aldehyde to health is not clear assurveillanceas surveillance programs are missing to follow exposure and potential health effects. Due to ethanol use aldahyde aldehyde levels are slightly increasing in Brazil. Study in Chine, Guangzhou Medical Collage concluded: inhalation of aldehydes and ketones in the same quantity as that of in sampling site of biomass combustion smoke induces oxidative damage in mice lung. There is potential for concern about the effect of ethanol on the general population and on specific sensitive populations such as pregnant women, ALDH deficient individuals, and people taking medication that block ethanol oxidation at the acetaldehyde stage (e.g., disulfiram, used to treat alcoholics). Lack of data on the impacts of ethanol inhalation makes it impossible to provide a definitive answer, but there is a possibility that we need to consider sensitive subpopulations. When addressing some of the broader questions the extent to which this is a high-priority area in filling knowledge gaps is a key consideration.[14]

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4.23.2 BenzeneBenzene is colorlesscolourless, flammable, toxic liquid with a pleasant aromatic odor. It is a hydrocarbon, with formula C6H6. The simplest picture of the benzene molecule is a hexagon of six carbon atoms joined by alternating single and double bonds and each bearing one hydrogen atom[20]. However, modern studies have shown that the six carbon-carbon bonds are all of equal strength and distance; thus the double-bond electrons do not belong to any particular bonds but rather are delocalized about the ring, with the result that the strength of each bond is between that of a9

single bond and that of a double bond.Ok, but you can leave that out as well (too much detail for purpose of this study) Source of benzene in ambient air? Only natural sourcesSource of benzene in ambient air is mainly related to traffic. The use of the biodiesel blends led to significant reductions in the emissions of the the BTEX compounds (benzene, toluene, ethylbenzene and xylenes), by about 5%, 9% and 22% relative to the diesel fuel. Natural sources of benzene, which include gas emissions from volcanoes and forest fires, also contribute to the presence of benzene in the environment. Benzene is also present in crude oil and gasoline and cigarette smoke.[22]Formatted: Space Before: 0 pt, After: 0 pt, Don't adjust space between Latin and Asian text, Don't adjust space between Asian text and numbers Formatted: Font: (Default) Times New Roman, 12 pt, No underline, Font color: Auto

Concentrations

Gee and Sollars, Gioda et al, Colon et al and dos Santos et al[6]have reported and analized couple earlier measurements of benzene and other atmospheric BTEX (benzene, toluene, ethylbenzene and xylenes) for Sa~o Paulo, Rio de Janeiro and surrounding area. Different sample period and numbers of samples were taken. Table below will display summary of ambient benzene concentration in air of Rio de Janeiro and Sa~o Paulo. Table 5Month/yearRio de Janeiro Dec. 1995 Dec. 1998Mar. 1999 MayNov. 2000 Jun. and Nov. 1999 Jun. and Nov. 1999 20042005 Oct. 2005 Sa~o Paulo 19951996 Nov. 1998 Nov. 1998 Aug. 2001 Mar.Apr. 2004

LocationOne location Central business district (FEEMA) Av. Presidente Vargas Eight urban tunnels Four underground parking Av. Presidente Vargas Reboucas Tunnel #2 One location Cerqueira Cesar Tunel 9 de Julho Janio Quadros Tunnel Fourteen locations

Benzene/ppb

Number of samples11 3 13 8 4 94 5 6 2 3 14

Sample period24h 1min 1min 1min 6h 1h 2h Summa canister grab sample Summa canister grab sample 5min 1h

2.9 1.0 3.5 11.8 27.8 4.5 25 5.2 3.5 11.0 13.924.8 0.5

There are limited modern data for the BTEX compound concentrations in the urban areas of Brazil. These data(Table 5) are not greatly different from those concentrations observed in many other areas of the world. One would expect the concentrations of the BTEX compounds from vehicle emissions to be lower than in other areas, due to the much greater fraction of ethanol in vehicle fuels in Brazil.Impact of benzene10

Brief exposure (5-10 minutes) to very high levels of benzene in air (10,000-20,000 ppm) can result in death. Lower levels (700-3,000 ppm) can cause drowsiness, dizziness, rapid heart rate, headaches, tremors, confusion, and unconsciousness. In most cases, people will stop feeling these effects when they are no longer exposed and begin to breathe fresh air.[22] Eating foods or drinking liquids containing high levels of benzene can cause vomiting, irritation of the stomach, dizziness, sleepiness, convulsions, rapid heart rate, coma, and death. The health effects that may result from eating foods or drinking liquids containing lower levels of benzene are not known. If you spill benzene on your skin, it may cause redness and sores. Benzene in your eyes may cause general irritation and damage to your cornea. Benzene causes problems in the blood. People who breathe benzene for long periods may experience harmful effects in the tissues that form blood cells, especially the bone marrow. These effects can disrupt normal blood production and cause a decrease in important blood components. A decrease in red blood cells can lead to anemia. Reduction in other components in the blood can cause excessive bleeding. Blood production may return to normal after exposure to benzene stops. Excessive exposure to benzene can be harmful to the immune system, increasing the chance for infection and perhaps lowering the body's defense against cancer. Long-term exposure to benzene can cause cancer of the blood-forming organs. This condition is called leukemia. Exposure to benzene has been associated with development of a particular type of leukemia called acute myeloid leukemia (AML). The Department of Health and Human Services has determined that benzene is a known carcinogen (can cause cancer). Both the International Agency for Cancer Research and the EPA have determined that benzene is carcinogenic to humans. Exposure to benzene may be harmful to the reproductive organs. Some women workers who breathed high levels of benzene for many months had irregular menstrual periods. When examined, these women showed a decrease in the size of their ovaries. However, exact exposure levels were unknown, and the studies of these women did not prove that benzene caused these effects. It is not known what effects exposure to benzene might have on the developing fetus in pregnant women or on fertility in men. Studies with pregnant animals show that breathing benzene has harmful effects on the developing fetus. These effects include low birth weight, delayed bone formation, and bone marrow damage. We do not know what human health effects might occur after long-term exposure to food and water contaminated with benzene. In animals, exposure to food or water contaminated with benzene can damage the blood and the immune system and can cause cancer. [22] The International Agency for Research on Cancer (IARC) classified it as a potential carcinogenic type I. Then, the use of benzene is restricted to two situations. Firstly in synthetic processes, when benzene is an essential reagent and it is not possible to exchange for another one.Second situation is in the petrochemical industry, when present in the process of petroleum cracking. The toxicological effects related to benzene are non-lymphocytic leukemia, aplastic anemia, chromosome aberrance and bone marrow progressive degeneration. [15] The most common health effects that are associated with long term exposure to benzene are[29]:y yFormatted: Font: Times New Roman, 12 pt, No underline, Font color: Auto, English (U.K.), Superscript Formatted: Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5"

Acute Myelogenous Leukemia (AML) in which cancer cells are present in the blood and bone marrow. Acute Lymphocytic Leukemia (ALL) in which the cancer affects the cells that make the lymphocytes for the bone marrow.11

y

Chronic Myelogemour Leukemia (CML) in which the leukemia develops from the white blood cells reducing the bodys ability to fight disease and infection.

Some studies show that exposure to benzene can also cause menstrual problems in females and decrease the size of the ovaries. Through tests done on animals exposed to this chemical, it has been shown that it does cause small weight in infants and damage to bone growth and bone marrow. Studies are carried out on health effects that exposure to benzene could cause. Research has already pointed it to be a factor to many disorders and illnesses. Anyone working in occupations where there is an increased risk of exposure should contact a doctor for testing immediately. Because most of the symptoms could be common to other diseases, those exposed may drop them off as being insignificant health issues until it becomes too late. Inhalation Reference Concentration for Benzene: Critical effect Decreased lymphocyte count (Human occupational inhalation study of Rothman et al., 1996) Exposures* BMCL = 8.2 mg/m3 Uncertainty Factor 300 Modified Factor 1 RfC 3 x 10-2 mg/m3Formatted: Centered Formatted Table Formatted: Centered

*Conversion factors: MW = 78.11. BMCL = 7.2 ppm, 8-hour TWA. Assuming 25C and 760 mm Hg, BMCL (mg/m3) = 7.2 ppm x MW/24.45 = 23.0 mg/m3. BMCLADJ = 23.0 mg/m3 x 10 m3/20 m3 x 5 days/7days = 8.2 mg/m3. (The BMC was based on a benchmark response of one standard deviation change from the control mean.) BMCL = benchmark concentration (lower bound on BMC)

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Concentration of benzene in ambient air is low, could you find any information on long term impacts of low concentration (probably there is no study?)

4.33.3 PM 10Particulate matter is the sum of all solid and liquid particles suspended in air, many of which are hazardous. It is complex mixture of dust, pollen, soot, smoke, and liquid droplets. These particles come in different size ranges such as coarse, fine and ultrafine. They also vary in composition and origin. Particles are either directly emitted into the air by sources such as combustion processes and windblown dust, or formed in the atmosphere by transformation of emitted gases such as SO2. In Europe, sulphate and organic matter are the main components of particulate air pollution in terms of the mass of the particles. Mineral dust, nitrate, and soot can also be major components under certain conditions. [20]PM10 Concentrations

PM10 is produced mostly through combustion, or during different industrial processes. It can also be produced by natural, largely uncontrollable sources, such as wind carried dust and fires. Air pollution monitoring systems differ among the cities in Brazil. For example, So Paulo has 1412

automatic monitoring sites distributed all over the city, including neighbourhoods further from downtown. Meanwhile, Curitiba has two monitoring stations, but only one with complete and representative data that could be used to calculate a city wide average. Fortaleza was the only city where TSP was measured, while the others provided data on PM10. In nNext table shows under-fi ve and elderly population?? in sevenseveral monitoring sites recorded in Brazilian state capitals and mean annual air pollution levels.[13] Table 6 Observed PM in Rio de Janeiro and So Paulo[28] title, sourcePeriod*** City PM10 ( g/m3)** Monitoring sites (n)# 6 14 (12 in 2001; 10 in 2002)

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2000-2003 1998-2002

Rio de Janeiro So Paulo

55.5 49.8

** Annual mean; *** Years included in calculating the mean annual PM1 0; # Number of monitoring sites included in the study.

Table 6 shows descriptive data on the two cities, such as population by age group and observed air pollution levels. Rio de Janeiro had the highest mean PM10, followed by So Paulo in Brazil. Despite being listed as the most polluted State capitals, except for Rio de Janeiro other cities showed annual levels below the standard air quality for PM10 as specified by CONAMA (the National Environmental Council) [13], which is 50 g/m3. Looking at PM10 pollution in other big city like Beijing we can see some similarities of high concentrations but Beijing is in worse situation. In 2008 during Olympic Games taken measurements show that 20 days of 30 PM10 levels where higher then suggested by WHO air quality guideline (50 micrograms/cubic metre). They varied from 20 300 ( g/m3).Impact of PM 10 Found clear evidence of effects of PM10 on the occurrence of asthma symptom episodes, and to a lesser extent on cough and peak expiratory flow (PEF). [16] In Europe, long-term exposure to current ambient particulate matter concentrations may affect the lungs of both children and adults and may reduce life expectancy by a few months, mainly in subjects with pre-existing heart and lung diseases. When particulate matter is combined with other air pollutants, the individual effects of each pollutant are cumulated. In certain cases, especially for combinations of particulate matter with ozone or allergens, effects were shown to be even greater than the sum of the individual effects. When particulate matter interacts with gases, this interaction changes its composition and, therefore, its effects. In long-term studies, it has been suggested that socially disadvantaged and poorly educated populations respond more strongly in terms of mortality. PM exposure is also related to reduced lung growth in children. [17]

4.43.4 Ozone Ozone or O3 is a colourless, pungent, highly reactive gas, considered as a secondary pollutant (It is not emitted into the air directly). It is composed of three oxygen atoms. It is the principal component of smog, which is caused primarily by automobile emissions, predominantly in urban areas. The respiratory system is the primary target of this oxidant pollutant. Respiratory tract13

responses induced by ozone include reduction in lung function, aggravation of preexisting respiratory disease (such as asthma), increased daily hospital admissions and emergency department visits for respiratory causes, and excess mortality.[18] The degree of adverse respiratory effects produced by ozone depends on several factors, including concentration and duration of exposure, climate characteristics, individual sensitivity, preexistent respiratory disease, and socioeconomic status.Source of ozoneSource of ozone?Formatted: Font: Bold, No underline, Font color: Auto Formatted: Font: Bold Formatted: Font: Times New Roman, 12 pt, Bold, No underline, Font color: Auto

*Source: [28]

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Concentrations Looking at ozone measurements taken in 14 different spots of Sao Paulo the air quality standard for O3 has been exceeded during 116219 days year-1 between 1997 and 2002. Even the WHO 8 h average O3 standard (120 mg m -3) has been exceeded during 51151 days year-1 in this same period. The O3 air quality standard in the Sao Paulo metropolitan region was exceeded on 77 days in 2003, decreasing to 46 in 2006, and rebounding to 72 in 2007. The O3 air quality standard in Brazil is 160 mg m 3 (81 ppb) as a 1 h average not to be exceeded more than once per year. [6] Comparing Sao Paulo ozone levels to big city like Beijing, Sao Paulo stays as a winner. During Olympic year 2008 Beijing had lover O3 levels peaking just once over 82ppb[12] staying daily average 7 40 ppb. Impact of Ozone Human population studies at ozone levels currently observed in Europe have reached inconsistent conclusions regarding effects of ozone on the frequency of asthma. They have provided little evidence of long-term effects on lung cancer or mortality. However, results suggest that long-term ozone exposure may affect lung function growth in children.[18]

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The man-made ozone that forms in the troposphere is extremely toxic and corrosive. People who inhale ozone during repeated exposure may permanently damage their lungs or suffer from respiratory infections. Ozone exposure may reduce lung function or aggravate existing respiratory conditions such as asthma, emphysema or bronchitis. Ozone may also cause chest pain, coughing, throat irritation or congestion. The adverse health effects of ground-level ozone are particularly dangerous for people who work, exercise, or spend a lot of time outdoors during warm weather. Seniors and children are also at greater risk than the rest of the population, because people in both age groups are more likely to have reduced or not fully formed lung capacity. In addition to human health effects, ground-level ozone is also hard on plants and animals, damaging ecosystems and leading to reduced crop and forest yields Ground-level ozone also kills many seedlings and damages foliage, making trees more susceptible to diseases, pests and harsh weather. [23]

54 Air quality policiesThe first move to control air pollutant emissions in Brazil was the issue of the government Edict nr 0231 of April 27th, 1976 of Ministry of Home Affairs.[24] In this edict, emission standards were used to establish the maximum permitted concentration levels in order to protect population and set goals that should be attained through local air pollution control plans.These standards were extracted from the US legislation (the most advanced in the world, then) and conformed little to the Brazilian reality, as they did not include a continuous air quality follow-up system, needed to attribute a dynamic character to the environment control. The first attempt in Brazil to control pollution emissions from automobiles directly was by The Vehicle AirPollution Control Programme (PROCONVE). It was later turned into a law. PROCONVE was, in fact. It defined targets for emission controls in new cars for the period 1988-97.[25] PRONAR - National Program for Air Quality Control (Programa Nacional de Controle de Qualidade do Ar) was launched 1989 and the federal government aimed at reducing the negative effects of atmospheric pollution on environment in the whole country. The main target of the resolution was to restrict the pollutant levels per atmospheric pollution source, limiting emissions nationwide, considering source typology and primary pollutants and using air quality standards as a complementary strategy. In table 7 summary of the legislation for atmospheric pollution control in Brazil is displayed. Table 7[24]Year1976

LawEDICT NR. 0231 OF 04/27/76 OF M.H.A. RESOLUTION NR. 05/89 OF CONAMA* RESOLUTION NR. 03/90 CONAMA

DescriptionEstablishes maximum permitted air concentrations to certain atmospheric pollutants in order to protect health. Standards based on us legislation. Institutes PRONAR aiming at limiting pollutant emission levels per pollution source. Spares the use of quality standards as complementary strategy. Resolution nr. 03/90 Substitute for edict 0231 of 1976, setting new quality

1989

1990

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1990

RESOLUTION NR. 08/90 OF CONAMA

standards. Sets maximum limits of pollutant emissions in air for stationary sources that function with external combustion according to the nominal potency

* CONAM - Environment National Advisory Board (Conselho Nacional do Meio Ambiente )

Comparesment Comparison of pollutants between Brazil and EU are shown in Table 8. Table 8 Pollutant Aldehyde/g km-1 Benzene g/m3 PM10 g/m3 O3 g/m3*

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Limits in Brazil 0.03 0.02 10 50 160***

Limits in EU Not yet required emissions limits 5 (average period 1 year) 50 (average period 24h), 40 (1 year) 120**(average period maximum daily 8 hour mean)

* Light duty vehicle exhaust emissions limits for 2007 and 2009 ** Permitted exceedances each year 25days average over 3 years

Couple of years ago the CONAMA enacted Resolution No. 382/06[26] which provides new standards regarding stationary emission sources. The Resolution provides for certain criteria to monitor atmospheric emissions, as well as emission standards applicable to specific stationary sources that generate heat, such as those related to activities concerning natural gas, oil and petroleum, sugar cane bagasse, wood, paper and mill, lead, aluminum, glass, cement, fertilizers, phosphoric acid, sulfuric acid, nitric acid and iron. This Resolution applies to new stationary emission sources, for which respective installation licenses were required from January 2, 2007. Same as Brazil EU has acknowledged that pollution damages human health and the environment. Since the late 1970s the European Union has recognised air pollution as one of Europes main political concerns. The Community is working at many levels to reduce exposure to air pollution: through legislation, through work on a wider international, through collaboration with sectors responsible for air pollution and with national, regional authorities and NGOs, and through research. The European Union policy on air quality aims to develop and implement appropriate instruments to improve air quality. Some later legislations and directives in the air-quality policy sector were introduced: Table 9 Year1996

LawThe Framework Legislation - The Air Quality Framework Directive 96/62/EC on ambient air quality assessment and management. Directive 1999/30/EC*

DescriptionThe Air Quality Framework Directive and the four Daughter Directives deifi ne the legislative basis for assessment and management of air quality in Member States. The Framework Directive gives general requirements and the Daughter Directives specify the requirements for the various pollutants in more detail. An important goal of the directives is that air quality be assessed and managed in a comparable way and on the basis of the same criteria in all Member States. Relating to limit values for sulphur dioxide (SO2), nitrogen dioxide (NO2), oxides of nitrogen (NOX), particulate matter (PM10) and lead (Pb) in ambient air. Relating to limit values for benzene and carbon monoxide in ambient air. Relating to ozone in ambient air. Relating to arsenic, cadmium, mercury, nickel and polycyclic aromatic

1999

2000 2002 2004

Directive 2000/69/EC* Directive 2002/3/EC* Directive 2004/107/EC*

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2001 2001 1998

Directive 2001/81/EC Directive 2001/80/EC Directive 98/69/EC

hydrocarbons in ambient air. National emission ceilings for certain atmospheric pollutants (the NEC Directive). the limitation of emissions of certain pollutants into the air from largecombustion plants (the LCP Directive). Relating to measures to be taken against air pollution by emissions from motorvehicles and amending Directive 70/220/EEC.Directive 98/70/EC relating to the quality of petrol and diesel fuels and amending the Directive 93/12/EEC on diesel fuels.

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65 Conclusions and recomendationsrecommendationsPollution concentrations in air have been quite quickly increasing in the major urban areas of Brazil caused mainly by the growing use of vehicles. Policies to control pollutant emissions in Brazil have relied basically on mandatory emission standards and subsidies for specific cleaner technology resulting in decrease of car emission rates. Though introduction of ethanol as a fuel or blend in fuel for cars and its considerable amount of usage shows increasing presents of aldehydes in air what rises a new problems. Peak formaldehyde concentration, for example, have been reported to have reached 151 ppb in Rio de Janeiro which may be one of the highest levels recorded in ambient air. PROCONVE protocol was successfully implemented and average emission levels of new cars was concluded being decreased considerably. In some studies it have been reported , for example, hydrocarbon emissions decrease by approximately92% for gasoline and 84% for ethanol cars, between 1988 and 1997.[25] In sum, thePROCONVE mandatory emission standards were an effective command-and-controltool for fighting and reducing pollutant emission levels from traffic. Growing fossil fuel prices world wild are rising and recently suggestions have been pointing out alternative fuels including ethanol, methanol or methane instead of fossil fuels what may help to improve the current conditions of air pollution. Though there are not many studies done regarding ethanol fuel created emissions. Decisions on whether the government should implement a complete/comprehensive surveillance program to follow exposure and potential health effects as ethanol use is increased should not be made until some risk assessment work is done.In 2016 Rio de Janeiro will hold Olympic Games and air quality will be a major determinative whether they are successful or not. As we recall Beijing 2008 games a lot of cyclists and long distance runners were complaining about problems toperform at their best due to low air quality. Further regular air monitoring program implementation by government and policy adjusting to higher standards would be advisable. OK!

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76 Bibliography[1]Mugnier, Clifford (January 2009). Grids & Datums Federative Republic of Brazil. http://www.asprs.org/resources/GRIDS/01-2009-brazil.pdf.Retrieved 2010-12-03.17

[2]"Geography of Brazil". Central Intelligence Agency. 2008. https://www.cia.gov/library/publications/the-world-factbook/geos/br.html. Retrieved 2010-1203. [3]"People of Brazil". Central Intelligence Agency. 2008. https://www.cia.gov/library/publications/the-world-factbook/geos/br.html. Retrieved 2010-1203. [4] http://tonto.eia.doe.gov/cfapps/ipdbproject/IEDIndex3.cfm?tid=90&pid=44&aid=8 Retrieved 2010-12-03 [5] http://www.corrosion-doctors.org/AtmCorros/mapBrazil.htm Retrieved 2010-12-13 [6] Larry G. Anderson, Ethanol fuel use in Brazil: air quality impacts Retrieved 2010-12-01 [7] R. K. Niven, Renewable Sustainable Energy, 9, 535555. Retrieved 2010-12-13 [8] L. D. Martins, M. F. Andrade, E. D. Freitas, A. Pretto, L. V. Gatti, E. L. Albuquerque, E. Tomaz, M. L. Guardani, M. H. R. B. Martins and O. M. A. Junior, Environ. Sci. Technol., 2006, 40, 67226729, Retrieved 2010-12-03 [9] R. Godinho, W. Acquaviva and J. Romano, 11th Brazilian Congress for Environmental and Sanitation Engineering.pdf, at Fortaleza 1981, Retrieved 2010-12-13 [10] CETESB, Relat_orio de Qualidade do Ar no Estado de Sao Paulo 2006, http://www.cetesb.sp.gov.br/Ar/relatorios/RelatorioAr2006.zip, Retrieved 2010-12-21 [11] D. Grosjean, A. H. Miguel and T. M. Tavares, Atmos. Environ., 1990, 101106. [12] Ambient concentrations of aldehydes in relation to Beijing Olympic air pollution control measures.http://www.atmos-chem-phys-discuss.net/10/19737/2010/acpd -10-19737-2010.pdf, J. C. Gong, T. Zhu, M. Hu, L. W. Zhang, H. Cheng, L. Zhang, J. Tong, and J. Zhang Retrieved 2010-12-20 [13] Izabel Marcilio, Nelson Gouveia, Quantifying the impact of air pollution on the urban population of Brazil, 2007, Retrieved 2010-12-20 [14]http://www.hc-sc.gc.ca/ewh-semt/air/out-ext/effe/ethanol/index-eng.php, Retrieved 2010-1212 [15]http://www.scielo.br/scielo.php?pid=S0103-50532010000100018&script=sci_arttext . Retrieved 2010-12-19 [16]http://ehp03.niehs.nih.gov/article/fetchArticle.action?articleURI=info%3Adoi%2F10.1289% 2Fehp.0900844 , Retrieved 2010-12-24 [17]http://www.greenfacts.org/en/particulate-matter-pm/level-2/02-health-effects.htm#4 , Retrieved 2010-12-24 [18]http://coep.pharmacy.arizona.edu/air/air_quality/OZONE.pdf , Retrieved 2010-12-24 [19] The Columbia Encyclopedia, Sixth Edition.http://www.encyclopedia.com/doc/1E1aldehyde.html, Retrieved 2010-12-23 [20] http://www.encyclopedia.com/topic/benzene.aspx#2 , Retrieved 2010-12-24 [21]http://www.greenfacts.org/en/particulate-matter-pm/index.htm , Retrieved 2010-12-24 [22] http://www.eco-usa.net/toxics/chemicals/benzene.shtml , Retrieved 2010-12-18 [23]http://environment.about.com/od/ozonedepletion/a/whatisozone.htm , Retrieved 2010-12-2418

[24] Air quality management in the thermopower generation in Brazil, Marco Aurlio dos Santos, Manoel Gonalves Rodrigues, Retrieved 2010-12-12 [25] Automobile Pollution Control in Brazil, Claudio Ferraz and Ronaldo Seroa da Motta, 2000 http://www.premonline.nl/archive/17/doc/creed29e.pdf , Retrieved 2010-12-24 [26]http://www.bakernet.com/NR/rdonlyres/82804705-7F0C-4481-BFE5CEA378CA08BB/0/brazil_air_pollution_legislation.pdf , Retrieved 2010-12-20 [27] http://ec.europa.eu/environment/enlarg/pdf/pubs/air_en.pdf , Retrieved 2010-12-24 [28] I. Marcilio, Quantifying the impact of air pollution on the urban population of Brazil [29] http://www.epa.gov/iris/subst/0276.htm , Retrieved 2011-01-15 Wow! Impressive list and you also added the date when you retrieved the documents, great If you use a document (found on the internet), you can limit yourselves to provide author, title, date etc of document. You dont have to include the url as well.

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