Minimization of the environmental impact in the unhairing of bovine hides

This study tests an alternative method to the traditional unhairing method used during the process of tanning the hides. The new method is based on the substitution of sodium sulfide by hydrogen peroxide as an unhairing agent in both hair recovery and recirculation of the floats employed in the process. The properties of the hides obtained using the two methods have been compared and the results indicate that those hides have similar physical, chemical, and organoleptic properties. However, the differences existing from an environmental point of view are significant. These include reductions of water consumption (approx 70%), chemical oxygen demand (approx 35%), toxicity (98%) and total kjendhal nitrogen (50%). Also, the risk associated with the production of hydrogen sulfide is eliminated, which implies a great improvement in terms of safety for the workers. Given the large amounts of water and chemical pollution discharged in the process, the reductions in absolute values represent a significant improvement. A financial assessment was carried out to demonstrate that the proposed new system is 16% more economic than the traditional one.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.     

Mutagenic and recombinagenic activity of airborne particulates, PM10 and TSP, organic extracts in the Drosophila wing-spot test

The genotoxicity associated with air pollution in the city of Canoas, Rio Grande do Sul (Brazil), was assessed in November (spring) and January (summer). We applied the somatic mutation and recombination test (SMART) in Drosophila melanogaster in its standard version with normal bioactivation (ST) and in its variant with increased cytochrome P450-dependent biotransformation capacity (HB). The data indicated the genotoxicity of TSP and PM10 collected in November, in both ST and HB crosses. The genotoxic activity of the PM10 material in the spring sample was exclusively associated with the induction of mitotic recombination, whereas the TSP genetic toxicity was due to both recombinational as well as point and/or chromosomal mutation events. Considering PM10 collected in January, a positive response--100% (17.10 m3/ml) concentration--was observed in the HB cross, which was not detected in the ST cross.     

Field scale characterization and modeling of contaminant release from a coal tar source zone

A coal tar contaminated site was characterized using traditional and innovative investigation methods. A careful interpretation of hydrogeological and hydrogeochemical data allowed for the conceptualization of the heterogeneous coal tar distribution in the subsurface. Past and future contaminant release from the source zone was calculated using a modeling framework consisting of a three-dimensional steady-state groundwater flow model (MODFLOW) and two hydrogeochemical models (MIN3P). Computational time of long-term simulations was reduced by simplifying the coal tar composition using 3 composite and 2 individual constituents and sequential application of a 2D centerline model (for calibration and predictions) and a 3D model (only for predictions). Predictions were carried out for a period of 1000 years. The results reveal that contaminant mass flux is governed by the geometry of zones containing residual coal tar, amount of coal tar, its composition and the physicochemical properties of the constituents. The long-term predictions made using the 2D model show that even after 1000 years, source depletion will be small with respect to phenanthrene, 89% of initial mass will be still available, and for the moderately and sparingly soluble composite constituents, 60% and 98%, respectively.     

Guidance note: risk management of workers with medical electronic devices and metallic implants in electromagnetic fields.

Medical electronic devices and metallic implants are found in an increasing number of workers. Industrial applications requiring intense electromagnetic fields (EMF) are growing and the potential risk of injurious interactions arising from EMF affecting devices or implants needs to be managed. Potential interactions include electromagnetic interference, displacement, and electrostimulation or heating of adjacent tissue, depending on the device or implant and the frequency of the fields. A guidance note, which uses a risk management framework, has been developed to give generic advice in (a) risk identification--implementing procedures to identify workers with implants and to characterise EMF exposure within a workplace; (b) risk assessment--integrating the characteristics of devices, the anatomical localisation of implants, occupational hygiene data, and application of basic physics principles; and (c) risk control--advising the worker and employer regarding safety and any necessary changes to work practices, while observing privacy.     

Modelling municipal solid waste generation: a review

The objective of this paper is to review previously published models of municipal solid waste generation and to propose an implementation guideline which will provide a compromise between information gain and cost-efficient model development. The 45 modelling approaches identified in a systematic literature review aim at explaining or estimating the present or future waste generation using economic, socio-demographic or management-orientated data. A classification was developed in order to categorise these highly heterogeneous models according to the following criteria--the regional scale, the modelled waste streams, the hypothesised independent variables and the modelling method. A procedural practice guideline was derived from a discussion of the underlying models in order to propose beneficial design options concerning regional sampling (i.e., number and size of observed areas), waste stream definition and investigation, selection of independent variables and model validation procedures. The practical application of the findings was demonstrated with two case studies performed on different regional scales, i.e., on a household and on a city level. The findings of this review are finally summarised in the form of a relevance tree for methodology selection.     

Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between (12)CH(4), (13)CH(4), and (12)CH(3)D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7vol% in the concentration and a RMSD of 0.8 per thousand in the delta(13)C value, with delta(13)C the relative (13)C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.