Rivelino M. Cavalcante

The impact of urbanization on tropical mangroves (Fortaleza, Brazil): Evidence from PAH distribution in sediments

This investigation represents the first environmental diagnosis of the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from a tropical mangrove in Fortaleza, northeastern Brazil. Sediment cores from six sampling stations in the Cocó and Ceará Rivers were retrieved in June-July 2006 to determine 17 priority PAHs. The total PAH concentrations (Sigma(PAHs)) ranged from 3.04 to 2234.76 microg kg(-1)(Cocó River) and from 3.34 to 1859.21 microg kg(-1) (Ceará River). These levels are higher than those of other cities with more industrial development. PAH concentrations did not reach probable effect levels (PELs). However, from 4.5 to 87.5% of individual PAH concentrations can occasionally cause adverse biological effects for aquatic organisms. The PAH molecular ratios indicate that the PAHs in the sediment core were derived mainly from petroleum, wood, and charcoal combustion (pyrogenic source), and that atmospheric deposition and urban runoff may serve as important pathways for PAH input to the sediment. Clearly, the Sigma(PAHs) in sediments collected in the Cocó and Ceará Rivers indicate that ongoing pollution is more severe than past pollution.

Evaluation of a low-cost adsorbent for removal of toxic metal ions from wastewater of an electroplating factory.

In this study, sugar cane residue or bagasse was used for removal of toxic metal ions from wastewater of an electroplating factory located in northeast Brazil. Prior acid treatment increased the adsorption efficacies in batch wise experiments. The microstructure of the material before and after the treatment was investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy. Column operations showed that removals of Cu(2+), Ni(2+) and Zn(2+) from wastewater (in the absence of cyanide) were 95.5%, 96.3.0%, and 97.1%, respectively. Regeneration of the adsorbent obtained in acid indicated that the efficiencies decreased only after the fourth cycle of re-use. Acid-treated sugar cane bagasse can be considered a viable alternative to common methods to remove toxic metal ions from aqueous effluents of electroplating industries.

Uso da casca de coco verde como adsorbente na remoção de metais tóxicos

Green coconut shells were treated with acid, base and hydrogen peroxide solutions for 3, 6, 12 and 24 h for removing toxic metals from synthetic wastewater. The removal of ions by the adsorbent treated with 0.1 mol L-1 NaOH/ 3h was 99.5% for Pb2+ and 97.9% for Cu2+. The removal of Cd2+, Ni2+, Zn2+, using adsorbent treated with 1.0 mol L-1 NaOH/3 h, was 98.5, 90.3 and 95.4%, respectively. Particle size, adsorbent concentration and adsorption kinetics were also studied. An adsorbent size of 60-99 mesh and a concentration of 30-40 g/L for 5 min exposure were satisfactory for maximum uptake of Pb2+, Ni2+, Cd2+, Zn2+ and Cu2+ and can be considered as promising parameters for treatment the aqueous effluents contaminated with toxic metals.

Técnicas de extrações e procedimentos de clean-up para a determinação de hidrocarbonetos policílicos aromáticos (HPA) em sedimentos da costa do Ceará

Extraction and clean-up are essential points in polycyclic aromatic hydrocarbon (PAHs) analysis in a solid matrix. This work compares extraction techniques and clean-up procedures for PAH analysis. PAH levels, their toxicological significance and source were also evaluated in the waters of the Coco and Ceara rivers. The efficiency of PAH recovery was higher for the soxhlet and ultrasonic techniques. PAH recovery varied from 69.3 to 99.3%. Total PAH concentration (ΣHPA) varied from 720.73 to 2234.76 µg kg-1 (Coco river) and 96.4 to 1859.21 µg kg-1 (Ceara river). The main PAH sources are pyrolytic processes and the levels were classified as medium so that adverse effects are possible.

Exposure Assessment for Formaldehyde and Acetaldehyde in the Workplace

Personal exposure and possible cancer risk to formaldehyde and acetaldehyde were appraised in 8 work places at a university in Brazil. Levels of formaldehyde measured ranged from 22.5 to 161.5 μg·m−3 and from 18.3 to 91.2 μg·m−3 for acetalde-hyde. The personal exposure, expressed as the potential dose in indoor air, was calculated to range from 129.8 to 930.4 μg·day−1 (low exposure) and 183.9 to 1318.1 μg·day−1 (medium exposure) for formaldehyde and 105.5 to 525.3 μg·day−1 (low exposure) and 149.5 to 744.2 μg·day−1 (medium exposure) for acetaldehyde. The indoor/outdoor ratio showed the existence of indoor sources of the compounds which were mainly in practical classes and research laboratories. The highest formaldehyde and acetaldehyde levels were found where chemical reagents were manipulated. Relating the levels found to the permissible limit given by the US OSHA showed there was no particular risk although some formaldehyde levels did exceed the lower exposure limit of the US agency NIOSH. Any cancer risk would be highest for female technicians and teaching researchers.

The legacy of organochlorine pesticide usage in a tropical semi-arid region (Jaguaribe River, Ceará, Brazil): Implications of the influence of sediment parameters on occurrence, distribution and fate.

Between the 1940s and 1990s, immeasurable amounts of organochlorine pesticides (OCPs) were used in endemic disease control campaigns and agriculture in the tropical semi-arid regions of Brazil. The present study evaluated the legacy of banned OCP usage, considering the levels, ecological risk and dependence on sediment physicochemical properties for the fate and distribution in the Jaguaribe River. The sum concentration of OCPs (ΣOCPs) ranged from 5.09 to 154.43 ng·g(-1), comparable to the levels found in other tropical and subtropical regions that have traditionally used OCPs. The environmental and geographical distribution pattern of p,p-DDT, p,p-DDD and p,p-DDE shows that the estuarine zone contained more than 3.5 times the levels observed in the fluvial region, indicating that the estuary of the Jaguaribe River is a sink. The temporal pattern indicates application of dichloro-diphenyl-trichloroethanes (DDTs) in the past; however, there is evidence of recent input of these pesticides. High ecological risk was observed for levels of γ-hexachlorocyclohexanes (γ-HCH) and heptachlor, and moderate ecological risk was observed for levels of DDTs in sediments from the Jaguaribe River. The heptachlor, γ-HCH and hexachlorobenzene (HCB) concentrations depend on the organic and inorganic fractions of sediment from the Jaguaribe River, whereas the p,p-DDE, p,p-DDD, p,p-DDT and α-endosulfan concentrations depend solely on the organic fraction of the sediment.

Influence of urban activities on polycyclic aromatic hydrocarbons in precipitation: Distribution, sources and depositional flux in a developing metropolis, Fortaleza, Brazil

We measured polycyclic aromatic hydrocarbons (PAHs) in bulk precipitation in the Fortaleza metropolitan area, Ceará, Brazil, for the first time. Because little information is available concerning PAHs in tropical climatic regions, we assessed their spatial distribution and possible sources and the influence of urban activities on the depositional fluxes of PAHs in bulk precipitation. The concentrations of individual and total PAHs (Σ(PAHs)) in bulk precipitation ranged from undetectable to 133.9 ng.L(-1) and from 202.6 to 674.8 ng.L(-1), respectively. The plume of highest concentrations was most intense in a zone with heavy automobile traffic and favorable topography for the concentration of emitted pollutants. The depositional fluxes of PAHs in bulk precipitation calculated in this study (undetectable to 0.87 μg.m(-2).month(-1)) are 4 to 27 times smaller than those reported from tourist sites and industrial and urban areas in the Northern Hemisphere. Diagnostic ratio analyses of PAH samples showed that the major source of emissions is gasoline exhaust, with a small percentage originating from diesel fuel. Contributions from coal and wood combustion were also found. Major economic activities appear to contribute to pollutant emissions.

Relation factor: A new strategy for quality control in the determination of pesticides in environmental aqueous matrices

The effects promoted by environmental aqueous matrices on pesticide determinations have been assessed, and for the first time, a simple, low-cost and efficient strategy for the correction of analytical results has been determined. This method can be useful as a parameter of quality control in a quality assurance programs. Evaluation of the matrix effect showed that environmental aqueous matrices, e.g., estuarine water, promote a distinctive and significant effect on the determination of pesticides. The picloram, atrazine and methyl parathion pesticides suffered the smallest effects promoted by the estuarine matrix, whereas chlorpyrifos and cypermethrin suffer a significant effect. For picloram, the matrix effect was a function of its physiochemical properties. However, for atrazine, methyl parathion, chlorpyrifos and cypermethrin, the matrix effect was promoted by environmental matrix components. As strategy for analytical quality control, it has been determined that there are relation factors (RFs) between pesticides and the selected surrogates standards. These RFs are not altered by the complexities and compositions of simple and complex aqueous matrices. Predetermined RFs was applied to the picloram, atrazine and methyl parathion assessment in a real sample from the estuary of the Jaguaribe River, and the results showed that when no quality control was applied, the concentration levels would be underestimated, leading to incorrect results and inaccurate conclusions.

UTILIZAÇÃO DA EXTRAÇÃO EM FASE SÓLIDA (SPE) NA DETERMINAÇÃO DE HIDROCARBONETOS POLICÍCLICOS AROMÁTICOS EM MATRIZES AQUOSAS AMBIENTAIS

Polycyclic aromatic hydrocarbons (PAHs) are a great environmental concern mainly because of their toxic, mutagenic and carcinogenic potential. This paper reports utilization of the solid-phase extraction (SPE) technique to determine PAHs in environmental aqueous matrices. The recovery from environmental aqueous matrices fortified with PAHs varied from 63.7 to 93.1% for atmospheric liquid precipitation, from 38.3 to 95.1% for superficial river water, and from 71.0 to 95.5% for marine water. No negative matrix effect was observed for the recovery of PAHs from atmospheric liquid precipitation and marine water, but was observed for superficial river water, particularly for PAHs possessing 5 and 6 aromatic rings.

4-Hydroxy-2,5-dimethylphenyl-benzophenone: Conformational stability, FT-IR and Raman investigation

In this paper we have studied the 4-hydroxyl-2,5 dimethylphenyl-benzophenone. Also, it was analyzed the vibrational assignment (FT-IR and Raman) in conjunction with computational results. The conformational analysis showed three barrier heights where two are due to the dihedral rotation and the other one is attributed to hydroxyl rotation. While the high dihedral rotational barrier (TS1) is 6.06-7.22 kcal mol(-1), the lower one (TS2) is almost three times smaller. The variations with the change of basis set is 5-8% to TS1, and 3-15% in the values predicted to TS2. In the case of OH rotational barrier, the values range from 3.70 to 4.86 kcal mol(-1), and it is also observed that this transition state is less sensitive to the change of basis set and to the method. Two isomers was detected due to the changes in the OH rotation with the gap energy lower than 0.7 kcal mol(-1), and at this point is seen that semi-empirical methods fail into describe the most stable conformation which may be due to the small energy gap. The enthalpy formation at 0 K and 298 K was 111.71 and 102.20 kcal mol(-1), respectively.