Reusing fly ash in glass fibre reinforced cement: a new generation of high-quality GRC composites

New composite materials based on an alkali-resistant glass-fibre reinforced cement (AR-GRC) system are being developed by using fly ash (FA) produced at coal thermoelectric power plants, and fluid catalytic cracking catalyst residue (FC3R) from the petrol industry as cement replacement materials. These wastes are reactive from the pozzolanic viewpoint, and modify the nature and the microstructure of the cement matrix when a part of the Portland cement is replaced in the formulation of GRC. Several microstructural and mechanical aspects are being studied for AR-GRC systems. The behaviour of composites exposed to ageing shows that the pozzolanic activity of the ground FA added in high amounts and its mixture with the FC3R increase the flexural strength and no evidences of strength decay are observed. Additionally, the fibres due to the high alkalinity of the cementing matrix can be deteriorated. Fibres in the control (only Portland cement) and FC3R containing composites were attacked, whereas composites with FA and their mixture with FC3R show that the fibres have not been attacked, due to the pozzolanic activity of replacing materials that reduce the calcium hydroxide content in the cementing matrix.     

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.     

Development and verification of a toxicokinetic model of polychlorinated biphenyl elimination in persons working in a contaminated building

BACKGROUND: Polychlorinated biphenyls are toxic and slowly degrading substances that have been in widespread industrial use in the 1960s and 1970s. Despite a worldwide reduction, environmental exposure remains an issue; the assessment of an individual's level of exposure at a given time in retrospect requires valid toxicokinetic modeling of the different PCB congeners. OBJECTIVES: To develop and verify a toxicokinetic model of the in vivo-degradation of PCB 28 and 52 in adult humans. METHODS: The plasma concentrations of PCB congeners were measured in 583 persons working in a contaminated building for an average of 14.7+/-9.6 years. The values were adapted to a simple pharmacokinetic model (yt = y0 x (1 - e(-kt))); the steady state concentration y0 was estimated based on the median values of persons working exposed more than 10 years. RESULTS: The steady state concentration of PCB 28 was 0.10 microg/l, that of PCB 52 0.02 microg/l. The half-life of the congeners was estimated based on a logarithmic regression analysis according to the model mentioned above; it was 2.18 (95% CI: 1.91-2.54) years for PCB 28 and 3.95 (95% CI: 3.55-4.45) years for PCB 52, respectively. Stepwise elimination of persons with very long employment duration did not reduce the estimated half-life. CONCLUSIONS: The estimated half-life is higher than previously published data especially for PCB 52. Possible reasons and implications of this finding are discussed.     

Changes in hematological and serum biochemical values in jundiá Rhamdia quelen due to sub-lethal toxicity of cypermethrin

Jundiá (Rhamdia quelen, Quoy and Gaimard), a South American teleostean fish, was exposed to sub-lethal concentrations of cypermethrin (30% and 45% of the 48-h LC(50) value of 0.265 ppm) for 2, 4 or 8 days. Serum biochemical and hematological values and behavioral changes were studied. The 30% LC(50), 0.08 ppm, produced significant increases in Mg(2+), P, K(+), creatinine, urea, glucose, cholesterol, aspartate aminotransferase and alkaline phosphatase levels, and reduction in total proteins and triglycerides in serum. The 45% LC(50), 0.12 ppm, produced significant increase in Na(+), Mg(2+), P, K(+), creatinine, urea, glucose, cholesterol, and alkaline phosphatase, and reduction in triglycerides and alanine aminotransferase levels in serum. At this concentration, the fish showed behavior changes such as hyper-excitability, asphyxia, and widening of mouth and operculum. The hematological values remained normal, except for hemoglobin concentrations and the mean corpuscular hemoglobin concentration, which increased with exposure to 0.08 ppm and 0.12 ppm cypermethrin. Results of the present work show that biochemical analysis of serum can be useful to detect incipient cypermethrin intoxication of the shoal.     

Fluorescence fingerprints and Cu2+-complexing ability of individual molecular size fractions in soil- and waste-borne DOM

Land spreading of organic materials introduces large amounts of dissolved organic matter (DOM) into the soil. DOM has the ability to form stable complexes with heavy metals and can facilitate their transport towards the groundwater. The effects on soil processes are difficult to assess, because different DOM components might react differently towards metal ions. The objective of this study was to investigate the fluorescence signature and the Cu2+-binding capacity of individual molecular size fractions of DOM from various sources. DOM extracted from leaf compost, chicken manure, sugar cane vinasse and a fulvic hypercalcaric cambisol was fractionated by the means of dialysis into four molecular size classes: MW<500, 50012000-14000 Da. Vinasse and leaf compost contained around 80% and 70%, respectively, of the total organic carbon in the fractions with low molecular weight (MW<3500 Da); in chicken manure and soil these fractions accounted for 40% and 50% only. Fluorescence was highest in the fraction MW>12000 Da for leaf compost, chicken manure and soil. The opposite result was obtained for vinasse, where the fractions with low molecular weight showed highest fluorescence intensities, distinguishing it from all other samples. Vinasse showed the greatest ability to bind Cu2+ with a resulting complex concentration of 6.31mgl(-1) while in contact with an excess of Cu2+. Leaf compost, soil and chicken manure followed with 2.69, 1.12, and 0.85mgl(-1), respectively. Within vinasse, the fraction MW<500 Da was able to form the most DOM-Cu complexes, indicating the importance of low molecular weight fractions in metal binding.     

Kinetic and adsorption study of acid dye removal using activated carbon

The adsorption of three acid dyes, Acid Red 97, Acid Orange 61 and Acid Brown 425 onto activated carbon was studied for the removal of acid dyes from aqueous solutions at room temperature (25 degrees C). The adsorption of each dye with respect to contact time was then measured to provide information about the adsorption characteristics of activated carbon. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The experimental isotherms obtained, except for Acid Orange 61 studied in mixture, were of the S-type in terms of the classification of Giles and co-workers. The best fit of the adsorption isotherm data was obtained using the Freundlich model. When a comparative study was made of the results obtained with single and mixed dyes, it can be seen that some of them affect others and modify their behavior in the adsorption process. The results indicate that activated carbon could be employed for the removal of dyes from wastewater.     

Mobility of dimethoate residues from spring broccoli field

Dimethoate [O, O-dimethyl-S-(N-methylcarbamoyl-methyl) phosphorodithioate] is a broad-spectrum systemic insecticide currently used worldwide and on many vegetables in Kentucky. Dimethoate is a hydrophilic compound (log KOW = 0.7) and has the potential of offsite movement from the application site into runoff and infiltration water. The dissipation patterns of dimethoate residues were studied on spring broccoli leaves and heads under field conditions. Following foliar application of Dimethoate 4E on broccoli foliage at the rate of 0.47 L acre(-1), dimethoate residues were monitored in soil, runoff water collected down the land slope, and in infiltration water collected from the vadose zone. The study was conducted on a Lowell silty loam soil (pH 6.9) planted with broccoli under three soil management practices: (i) soil mixed with municipal sewage sludge, (ii) soil mixed with yard waste compost, and (iii) no-mulch rototilled bare soil. The main objective of this investigation was to study the effect of mixing native soil with municipal sewage sludge or yard waste compost, having considerable amounts of organic matter, on off-site movement of dimethoate residues into runoff and infiltration water following spring rainfall. The initial deposits of dimethoate were 6.2 and 21.4 micro g g(-1) on broccoli heads and leaves, respectively. These residues dissipated rapidly and fell below the maximum residue limit of 2 micro g g(-1) on the heads and leaves after 10 and 14 d, respectively, with half-lives of 5.7 d on broccoli heads and 3.9 d on the leaves. Dimethoate residues detected in top 15 cm of soil (due to droplet drift and wash off residues from broccoli foliage) one day (d) following spraying, were 30.5 ng g(-1) dry soil in the sewage sludge treatment, and 46.1 and 134.5 ng g(-1) dry soil in the yard waste and no mulch treatments, respectively. Water infiltration was greater from yard waste compost treatment than from no mulch treatment, however concentrations of dimethoate in the vadose zone of the three soil treatments did not differ.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Acetylcholinesterase-polyaniline biosensor investigation of organophosphate pesticides in selected organic solvents

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State-Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, alpha and beta endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino-Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6% leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (alpha-endosulfan), 1.47E-162 (beta-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.