Acid Rain in Downtown São Paulo City, Brazil

During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown São Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, $ \rm NH^{ + }_{4} During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown S?o Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, , K⁺, Ca²⁺, Mg²⁺, Cl⁻, , ) and carboxylic acids (acetic, formic and oxalic) using ion chromatography. The volume weighted mean, VWM, of the anions , and Cl⁻ was, respectively, 20.3, 12.1 and 10.7 μmol l⁻¹. Rainwater in S?o Paulo was acidic, with 55% of the samples exhibiting a pH below 5.6. The VWM of the free H⁺ was 6.27 μmol l⁻¹), corresponding to a pH of 5.20. Ammonia (NH₃), determined as (VWM = 32.8 μmol l⁻¹), was the main acidity neutralizing agent. Considering that the H⁺ ion is the only counter ion produced from the non-sea-salt fraction of the dissociated anions, the contribution of each anion to the free acidity potential has the following profile: (31.1%), (26.0%), CH₃COO⁻ (22.0%), Cl⁻ (13.7%), HCOO⁻ (5.4%) and (1.8%). The precipitation chemistry showed seasonal differences, with higher concentrations of ammonium and calcium during autumn and winter (dry period). The marine contribution was not significant, while the direct vehicular emission showed to be relevant in the ionic composition of precipitation.     

Determination of selenium by GFAAS in slurries of fish feces to estimate the bioavailability of this micronutrient in feed used in pisciculture

This paper presents a simple, fast and sensitive method to determine selenium in samples of feces and of fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of selenium) were 0.31 microg l(-1) and 1.03 microg l(-1), respectively, for the standard feces slurries and 0.35 microg l(-1) and 1.16 microg l(-1), respectively, for the standard feed slurries. The proposed method was applied in studies of bioavailability of selenium in different fish feeds and the results proved consistent with that obtained from samples mineralized by acid digestion using the microwave oven.     

Modelling of PCDD/F release from MSW bio-drying

In the present work, an experimentation was carried out to study the behaviour of PCDD/F during the process of municipal solid waste (MSW) bio-drying. This process belongs to the biological mechanical treatment (BMT) options and is aimed to the dewatering of MSW thanks to the biological exothermal reactions (thermal drying, on the contrary, needs an external heat source as methane). The result is a decrease of waste weight and an increase of lower heating value (as the energy content refers to a lower amount of waste). Of course, the overall energy availability does not increase, but the characteristics of bio-drying are interesting as a way for refuse derived fuel generation: glass, metals and inert removals are easier after bio-drying. The literature of the sector shows only few data on PCDD/F emission to air from BMT. Anyway, in the present work an original theory has been put forward in order to explain the enrichment of PCDD/F in the air exiting the biological processes. The role of the initial PCDD/F concentration in the ambient air entering the plant is obviously taken into account. The results of the developed experimentation and the following elaborations point out that PCDD/F could be freed from the volatile solids consumed during the process. The different amount of PCDD/F in the waste and the different consumption of volatile solids depending on the biological process can explain the different PCDD/F emission factors available in the literature.     

Corrected first-order model of DEHP degradation

Corrected first-order model was applied to describe the biological removal of di-(2-ethylhexyl) phthalate (DEHP) in sludge-amended soil along with batch and continuous-flow anaerobic reactors with different initial/influent DEHP concentrations and hydraulic retention times. Only two kinetic parameters - the first-order rate coefficient k describing the overall kinetics of the process and the coefficient alpha characterizing the fraction of non-degradable DEHP - were used to fit the array of experimental data published earlier. The values of k and alpha estimated for DEHP removal from different sludges at 35 degrees C varied within the range of 0.03-0.07 d(-1) and 0.25-0.5, respectively. In sludge-amended soil, the first-order kinetic coefficient k increased from 0.007 to 0.028 d(-1) and the fraction of non-degradable DEHP alpha decreased from 0.6 to 0.5 with the increase in incubation temperature from 5 to 20 degrees C. The rate coefficient k increased by a factor of 2 when the temperature increased from 5 to 10 degrees C or from 10 to 20 degrees C.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Distribution of PAHs in Surface Soils from Petroleum Handling Facilities in Calabar

The level of concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface soils from petroleum handling facilities (kerosene tank, generating plant, petrol stations, mechanic workshops, leaking pipeline and air port fuel dump) from Calabar metropolis southeastern Nigeria was determined by gas chromatography/ mass spectrometry. The results show that total polycyclic aromatic hydrocarbons (PAHs) varied from 1.80 to 334.43 mg/kg with a mean of 50.31 mg/kg. The lowest value of 1.80 mg/kg was obtained from petrol station while the highest value of 334.43 mg/kg was obtained from facility characterised by petrol stations and mechanic workshops. The ratio of phenanthrene/anthracene and fluoranthene/pyrene, varied from 0.43 to 27.72 and from 0.14 to 17.76 respectively. These ratios indicate various sources for the PAH. The two to three ring PAHs are the most abundant. Based on the PAH ratios and content alone it is not possible to distinguish between contribution from motor vehicle exhaust, gasoline spillage, used engine oil or petroleum production. However, considering the area of the study, it is very likely that the major source of soil contamination is originating from petroleum product.     

A Procedure for NEPA Assessment of Selenium Hazards Associated With Mining

This paper gives step-by-step instructions for assessing aquatic selenium hazards associated with mining. The procedure was developed to provide the U.S. Forest Service with a proactive capability for determining the risk of selenium pollution when it reviews mine permit applications in accordance with the National Environmental Policy Act (NEPA). The procedural framework is constructed in a decision-tree format in order to guide users through the various steps, provide a logical sequence for completing individual tasks, and identify key decision points. There are five major components designed to gather information on operational parameters of the proposed mine as well as key aspects of the physical, chemical, and biological environment surrounding it — geological assessment, mine operation assessment, hydrological assessment, biological assessment, and hazard assessment. Validation tests conducted at three mines where selenium pollution has occurred confirmed that the procedure will accurately predict ecological risks. In each case, it correctly identified and quantified selenium hazard, and indicated the steps needed to reduce this hazard to an acceptable level. By utilizing the procedure, NEPA workers can be confident in their ability to understand the risk of aquatic selenium pollution and take appropriate action. Although the procedure was developed for the Forest Service it should also be useful to other federal land management agencies that conduct NEPA assessments, as well as regulatory agencies responsible for issuing coal mining permits under the authority of the Surface Mining Control and Reclamation Act (SMCRA) and associated Section 401 water quality certification under the Clean Water Act. Mining companies will also benefit from the application of this procedure because priority selenium sources can be identified in relation to specific mine operating parameters. The procedure will reveal the point(s) at which there is a need to modify operating conditions to meet environmental quality goals. By recognizing concerns early in the NEPA process, it may be possible for a mining company to match operational parameters with environmental requirements, thereby increasing the likelihood that the permit application will be approved.     

Using Spatial Pattern to Quantify Relationship Between Samples, Surroundings, and Populations

The need for accurate carbon budgeting, climate change modelling, and sustainable resource management has lead to an increase in the number of large area forest monitoring programs. Large area forest monitoring programs often utilize field and remotely sensed data sources. Sampling, via field or photo plots, enables the collection of data with the desired level of categorical detail in a timely and efficient manner. When sampling, the aim is to collect representative detailed data enabling the statistical reporting upon the characteristics of larger areas. As a consequence, approaches for investigating how well sample data represent larger areas (i.e., the sample neighbourhood and the population) are desired. Presented in this communication is a quantitative approach for assessing the nature of sampled areas in relation to surrounding areas and the overall population of interest. Classified Landsat data is converted to forest/non-forest categories to provide a consistent and uniform data set over a 130,000 km² study region in central British Columbia, Canada. From this larger study area 322 2 × 2 km photo plots on a 20 × 20 km systematic grid are populated with composition and configuration information for comparison to non-sampled areas. Results indicate that typically, within the study area, the spatial pattern of forest within a photo plot is representative of the forest patterns found within primary and secondary neighbourhoods and over the entire population of the study. These methods have implications for understanding the nature of data used in monitoring programs worldwide. The ability to audit photo and field plot information promotes an increased understanding of the results developed from sampling and provides tools identifying locations of possible bias.