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.

Intercontinental transport of nitrogen oxide pollution plumes

We describe the first satellite observation of intercontinental transport of nitrogen oxides emitted by power plants, verified by simulations with a particle tracer model. The analysis of such episodes shows that anthropogenic NOx plumes may influence the atmospheric chemistry thousands of kilometers away from its origin, as well as the ocean they traverse due to nitrogen fertilization. This kind of monitoring became possible by applying an improved algorithm to extract the tropospheric fraction of NO2 from the spectral data coming from the GOME instrument.As an example we show the observation of NO2 in the time period 4-14 May, 1998, from the South African Plateau to Australia which was possible due to favourable weather conditions during that time period which availed the satellite measurement. This episode was also simulated with the Lagrangian particle dispersion model FLEXPART which uses NOx emissions taken from an inventory for industrial emissions in South Africa and is driven with analyses from the European Centre for Medium-RangeWeather Forecasts. Additionally lightning emissions were taken into account by utilizing Lightning Imaging Sensor data. Lightning was found to contribute probably not more than 25% of the resulting concentrations. Both, the measured and simulated emission plume show matching patterns while traversing the Indian Ocean to Australia and show great resemblance to the aerosol and CO2 transport observed by Piketh et al. (2000).

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.

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.

Effects of dispersion by Gd3+ upon europium diphenylphosphinate luminescence

A series of binary diphenylphosphinates with Eu3+ and Gd3+ were prepared. The compounds have the general formula Gd1-xEux(DPP)(3), where x ranges from 0 to 1. The spectroscopic measurements show interesting behavior. The intensity of the D-5(0) --> F-7(2) transitions decreases relative to D-5(0) --> F-7(1) With an increase in europium dispersion. Inside the temporal domain, the same decrease is observed with increasing delay after excitation. The lifetimes are also affected, which can be seen in the x = 1 compound, where the decay is a first-order process and lifetime values are 4.81 ms. In the binary compound, as an effect of dispersion, the lifetime of the D-5(0) level measured at the D-5(0) --> F-7(1) transition increases with europium dispersion, and the average along the series is 6.25 ms. The decay measured at the D-5(0) --> F-7(2) transitions reveals a second-order process with lifetimes ranging from 1.90 to 6.00 ms. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Influence of Sources and Meteorology on Surface Concentrations of Gases and Aerosols in a Coastal Industrial Complex

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Joint control charts for monitoring location and dispersion

The T-2 and the generalized variance vertical bar S vertical bar charts are used for monitoring the mean vector and the covariance matrix of multivariate processes. In this article, we propose for bivariate processes the use of the T-2 and the VMAX charts. The points plotted on the VMAX chart correspond to the maximum of the sample variances of the two quality characteristics. The reason to consider the VMAX statistic instead of the generalized variance vertical bar S vertical bar is the user's familiarity with the computation of simple sample variances; we can't say the same with regard to the computation of the generalized variance vertical bar S vertical bar.

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.

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.

Dispersion relations and the spin polarizabilities of the nucleon

A forward dispersion calculation is implemented for the spin polarizabilities γ1, ⋯, γ4 of the proton and the neutron. These polarizabilities are related to the spin structure of the nucleon at low energies and are structure-constants of the Compton scattering amplitude at script O sign(ω3). In the absence of a direct experimental measurement of these quantities, a dispersion calculation serves the purpose of constraining the model building, and of comparing with recent calculations in heavy baryon chiral perturbation theory. © 1998 Elsevier Science B.V.

Update on atmospheric neutrinos

We discuss the impact of recent experimental results on the determination of atmospheric neutrino oscillation parameters. We use all published results on atmospheric neutrinos, including the preliminary large statistics data of Super-Kamiokande. We reanalyze the data in terms of both vμ → vτ and vμ → ve channels using new improved calculations of the atmospheric neutrino flux. We compare the sensitivity attained in atmospheric neutrino experiments with those of accelerator and reactor neutrino oscillation searches, including the recent CHOOZ experiment. We briefly comment on the implications of atmospheric neutrino data in relation to future searches for neutrino oscillations with long baselines, such as the K2K, MINOS, ICARUS, and NOE experiments.

An updated analysis on atmospheric neutrinos

We have reanalysed the atmospheric neutrino data including new results from Super-Kamiokande and Soudan-II experiments, under the assumption of two-flavor neutrino oscillation. We present the allowed region of oscillation parameters for the νμ → ντ channel. In performing this re-analysis we also take into account some recent theoretical improvements in the flux calculations.

Atmospheric neutrino observations and flavor changing interactions

Flavor changing (FC) neutrino-matter interactions can account for the zenith-angle-dependent deficit of atmospheric neutrinos observed in the SuperKamiokande experiment, without directly invoking either neutrino mass or mixing. We find that FC ν μ-matter interactions provide a good fit to the observed zenith angle distributions, comparable in quality to the neutrino oscillation hypothesis. The required FC interactions arise naturally in many attractive extensions of the standard model. © 1999 The American Physical Society.