Composição química das águas pluviais e deposição atmosférica anual na bacia do Alto Sorocaba (SP)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

PM2.5 and PM10: The influence of sugarcane burning on potential cancer risk

In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM2.5 and PM10) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM2.5 and PM10 fractions were collected using a dichotomous sampler (10 L min(-1), 24 h) with Teflon (TM) filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM2.5 in 2009) was 0.99 ng m(-3) (NHV) and 3.3 ng m(-3) (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m(-3) and 0.12 ng m(-3) for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaPeq), where the overall toxicity of a PAR mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaPeq median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m(-3) and 1.2-1.4 ng m(-3) for the NHV and HV seasons, respectively. Considering that the maximum permissible BaPeq in ambient air is 1 ng m(-3), related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern. (C) 2010 Published by Elsevier Ltd.

Indoor NO2 air pollution and lung function of professional cooks

Studies of cooking-generated NO2 effects are rare in occupational epidemiology. In the present study, we evaluated the lung function of professional cooks exposed to NO2 in hospital kitchens. We performed spirometry in 37 cooks working in four hospital kitchens and estimated the predicted FVC, FEV1 and FEF25-75, based on age, sex, race, weight, and height, according to Knudson standards. NO2 measurements were obtained for 4 consecutive days during 4 different periods at 20-day intervals in each kitchen. Measurements were performed inside and outside the kitchens, simultaneously using Palm diffusion tubes. A time/exposure indicator was defined as representative of the cumulative exposure of each cook. No statistically significant effect of NO2 exposure on FVC was found. Each year of work as a cook corresponded to a decrease in predicted FEV1 of 2.5% (P = 0.046) for the group as a whole. When smoking status and asthma were included in the analysis the effect of time/exposure decreased about 10% and lost statistical significance. on predicted FEF25-75, a decrease of 3.5% (P = 0.035) was observed for the same group and the inclusion of controllers for smoking status and asthma did not affect the effects of time/exposure on pulmonary function parameter. After a 10-year period of work as cooks the participants of the study may present decreases in both predicted FEV1 and FEF25-75 that can reach 20 and 30%, respectively. The present study showed small but statistically significant adverse effects of gas stove exposure on the lung function of professional cooks.

Study on the use of oxidant scrubbers for elimination of interferences due to nitrogen dioxide in analysis of atmospheric dimethylsulfide

Neste trabalho foi avaliado o desempenho de filtros para dióxido de nitrogênio, buscando evitar perdas durante a amostragem de sulfetos orgânicos, provocadas por oxidantes atmosféricos. Diferentes compostos e misturas foram usadas para recobrir superfícies sólidas empregadas na preparação destes filtros. Um sistema automatizado de análise em fluxo foi utilizado para comparar a eficiência de retenção de dióxido de nitrogênio pelos filtros. Entre os materiais testados na preparação dos filtros, as melhores escolhas foram papel ou lã de vidro impregnados com a mistura de sulfato de ferro (II), ácido sulfúrico e ácido pirogalico e ainda os filtros feitos de papel impregnados com trietanolamina. Os resultados obtidos em laboratório com mistura de gás padrão de dimetilsulfeto e experimentos em campo confirmaram a qualidade dos filtros e indicaram que eles podem ser utilizados para evitar a oxidação de sulfetos orgânicos durante a sua amostragem.

Fluorometric fiber optic drop sensor for atmospheric hydrogen sulfide

A fluorometric technique based on a liquid drop excited from its interior by an optical fiber is described for the measurement of low concentrations of atmospheric hydrogen sulfide (H2S). A drop of alkaline fluorescein mercuric acetate (FMA) solution is suspended in a flowing air sample stream and serves as a renewable sensor. An optical fiber contained within the conduit that forms the drop, brings in the excitation beam; the fluorescence emission is measured by an inexpensive photodiode positioned close to the drop. As H2S in the sample is collected by the alkaline drop, it reacts rapidly with FMA resulting in a significant decrease in fluorescence intensity, proportional to the concentration of H2S sampled. The chemistry of this uniquely selective reaction has been well established for many years, the present technique permits a simple fast inexpensive near real-time measurement with very little reagent consumption. Even without prolonged sampling/preconcentration steps, limits of detection (LODs) in the double digit ppbv range is readily attainable. (C) 1997 Elsevier B.V. B.V.

Sources of atmospheric acidity in an agricultural-industrial region of São Paulo State, Brazil

[1] Surface-based measurements of atmospheric formic acid (HCOOH), acetic acid (CH3COOH), sulfur dioxide (SO2), hydrogen chloride (HCl), and nitric acid (HNO3) were made in central São Paulo State, Brazil, between April 1999 and March 2000. Mean concentrations were 9.0 ppb (HCOOH), 1.3 ppb (CH3COOH), 4.9 ppb (SO2), 0.3 ppb (HCl), and 0.5 ppb (HNO3). Concentrations in sugar cane burning plumes were 1160-4230 ppb (HCOOH), 360-1750 ppb (CH3COOH), 10-630 ppb (SO2), 4-210 ppb (HCl), and 14-90 ppb (HNO3). Higher ambient concentrations of SO2, HCl and HNO3 were measured during the burning season (May-November). Concentrations of SO2 and HCl increased during the evening, and of HCOOH and CH3COOH were lowest in the morning, with peak levels in the afternoon. Ratios obtained between different species showed either nighttime maxima (SO2/HCOOH, SO2/CH3COOH, SO2/HNO3, CH3COOH/HNO3, SO2/HCl and HCOOH/HNO3), daytime maxima (HCOOH/HCl, CH3COOH/HCl and HNO3/HCl), or no clear trends (HCOOH/CH3COOH). Correlation analysis showed that SO2 and HCl were primary emissions from biomass burning and road transport; HCOOH, HNO3 and CH3COOH were products of photochemistry; HCOOH and CH3COOH were emitted directly during combustion as well as from biogenic sources. Biomass burning affected atmospheric acidity on a regional scale, while vehicular emissions had greater impact in urban and adjacent areas. Atmospheric ammonia levels were insufficient to neutralize atmospheric acidity, which was mainly removed by deposition to the surface.

Determination of aldicarb, aldicarb sulfoxide and aldicarb sulfone in some fruits and vegetables using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

An analytical method for the determination of aldicarb, and its two major metabolites, aldicarb sulfoxide and aldicarb sulfone in fruits and vegetables is described. Briefly the method consisted of the use of a methanolic extraction, liquid-liquid extraction followed by solid-phase extraction clean-up. Afterwards, the final extract is analyzed by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The specific fragment ion corresponding to [M-74](+) and the protonated molecular [M+K](+) ion were used for the unequivocal determination of aldicarb and its two major metabolites. The analytical performance of the proposed method and the results achieved were compared with those obtained using the common analytical method involving LC with post-column fluorescence detection (FL). The limits of detection varied between 0.2 and 1.3 ng but under LC-FL were slightly lower than when using LC-APCI-MS. However both methods permitted one to achieve the desired sensitivity for analyzing aldicarb and its metabolites in vegetables. The method developed in this work was applied to the trace determination of aldicarb and its metabolites in crop and orange extracts. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Measurement of atmospheric formaldehyde using a drop collector and in-situ colorimetry

A sensitive and affordable approach is described for the in-situ measurement of ambient formaldehyde. Air is sampled around a 100 microliter aqueous drop containing 3-methyl-2-benzothiazoline hydrazone. After a desired period of sampling (typ. 5 min) and a waiting period of 10 min for the reaction to be completed, a second reagent (FeCl3) is added to the drop by means of a conjoined conduit. A blue product is formed and is read after an additional 10 min of reaction by a fiber-optic/light emitting diode based photodetector. A fresh drop is then formed and the process begins anew. As demonstrated here, the limit of detection is similar to 6.25 mu g m(-3) HCHO but can be significantly improved by using longer sampling times and a sampling rate higher than 100 mi min(-1) used in most of this work. This is the first example of a chromogenic drop sensor that utilizes sequential reagent addition.

Yeasts and others parameters of pollution of the Ribeirao Claro stream in Rio Claro, São Paulo

The main water source of the Rio Claro municipal district (DAAE) was analysed for determining the level of organic contamination. Temperature, pH, light penetration, conductivity, dissolved oxygen, total dissolved phosphate, ortophosphate, ammonia, heterotrofic bacteria, total coliforms, fecal coliforms, total yeasts and fermentative yeasts were analysed during one year with samples being collected on a monthly basis. Bathing quality of the water from sites 1, 2 and 3 were classified, respectively, as Satisfactory, Very Good and Improper based on fecal coliform counts. Total yeast counts were appropriate as a complement for the appraisal of fresh water contamination by coliform counts. Seventeen yeast species belonging to genera Candida, Cryptococcus, Kloeckera, Pichia and Rhodotorula were found but none of them could be correlated with a level of contamination. Candida famata, C. robusta-like and C. colliculosa were isolated at all of the sites and between the five species found only at the more polluted site, Rhodotorula mucilaginosa was prevalent.

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.

A Semi-Continuous Analyzer for the Fluorimetric Determination of Atmospheric Formaldehyde

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influence of Intensive Agriculture on Dry Deposition of Aerosol Nutrients

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Atmospheric emission of reactive nitrogen during biofuel ethanol production

This paper evaluates emissions to the atmosphere of biologically available nitrogen compounds in a region characterized by intensive sugar cane biofuel ethanol production. Large emissions of NH(3) and NO,, as well as particulate nitrate and ammonium, occur at the harvest when the crop is burned, with the amount of nitrogen released equivalent to similar to 35% of annual fertilizer-N application. Nitrogen oxides concentrations show a positive association with fire frequency, indicating that biomass burning is a major emission source, with mean concentrations of NO, doubling in the dry season relative to the wet season. During the dry season biomass burning is a source of NH3, with other sources (wastes, soil, biogenic) predominant during the wet season. Estimated NO(2)-N, NH(3)-N, NO(3)(-)-N and NH(4)(+)-N emission fluxes from sugar cane burning in a planted area,of ca. 2.2 x 10(6) ha are 11.0, 1.1, 0.2, and 1.2 Gg N yr(-1), respectively.

Global and diffuse solar irradiances in urban and rural areas in southeast Brazil

The seasonal evolution of daily and hourly values of global and diffuse solar radiation at the surface are compared for the cities of São Paulo and Botucatu, both located in Southeast Brazil and representative of urban and rural areas, respectively. The comparisons are based on measurements of global and diffuse solar irradiance carried out at the surface during a six year simultaneous period in these two cities. Despite the similar latitude and altitude, the seasonal evolution of daily values indicate that São Paulo receives, during clear sky days, 7.8% less global irradiance in August and 5.1% less in June than Botucatu. on the other hand, São Paulo receives, during clear sky days, 3.6% more diffuse irradiance in August and 15.6% more in June than Botucatu. The seasonal variation of the diurnal cycle confirms these differences and indicates that they are more pronounced during the afternoon. The regional differences are related to the distance from the Atlantic Ocean, systematic penetration of the sea breeze and daytime evolution of the particulate matter in São Paulo. An important mechanism controlling the spatial distribution of solar radiation, on a regional scale, is the sea breeze penetration in São Paulo, bringing moisture and maritime aerosol that in turn further increases the solar radiation scattering due to pollution and further reduces the intensity of the direct component of solar radiation at the surface. Surprisingly, under clear sky conditions the atmospheric attenuation of solar radiation in Botucatu during winter - the biomass burning period due to the sugar cane harvest - is equivalent to that at São Paulo City, indicating that the contamination during sugar cane harvest in Southeast Brazil has a large impact in the solar radiation field at the surface.

Atmospheric cosmic rays in the South Atlantic anomaly region

To study the production and propagation of fast secondaries particles in the atmosphere, data collected during eleven quiet-time balloon flights are analysed. Comparisons of these data with those obtained in different geomagnetic rigidity regions permit to estimate the contributions of the proton and electron components in the measured intensities. Derivations of this last component in the «upward» and «downward» moving electrons fluxes indicate that in the anomaly region a fraction of these particles, produced by the primary protons, are leaving the atmosphere and will not return to the Earth. © 1991 Società Italiana di Fisica.