Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicide MCPA (4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leaf weeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and ¹H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH₂ group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD.

The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.     

Surface-sediment and hermit-crab contamination by butyltins in southeastern Atlantic estuaries after ban of TBT-based antifouling paints

Butyltin (BT) contamination was evaluated in hermit crabs from 25 estuaries and in sediments from 13 of these estuaries along about 2,000 km of the Brazilian coast. BT contamination in hermit crabs ranged from 2.22 to 1,746 ng Sn g^-1 of DBT and 1.32 to 318 ng Sn g^-1 of TBT. In sediment samples, the concentration also varied widely, from 25 to 1,304 ng Sn g^-1 of MBT, from 7 to 158 ng Sn g^-1 of DBT, and from 8 to 565 ng Sn g^-1 of TBT. BTs are still being found in surface sediments and biota of the estuaries after the international and Brazilian bans, showing heterogeneous distribution among and within estuaries. Although hermit crabs were previously tested as an indicator of recent BT contamination, the results indicate the presence of contamination, probably from resuspension of BTs from deeper water of the estuary.

Diphenyl diselenide attenuates hepatic and hematologic toxicity induced by chlorpyrifos acute exposure in rats

Purpose

In this study, we investigated the effect of diphenyl diselenide [(PhSe)₂] on chlorpyrifos (CPF)-induced hepatic and hematologic toxicity in rats.

Methods

Rats were pre-treated with (PhSe)₂ (5?mg/kg) via the oral route (oral gavage) once a day for 7?days. On the eighth and ninth days, rats were treated with (PhSe)₂ (5?mg/kg) 30?min prior to CPF (50?mg/kg, by subcutaneous route). The aspartate aminotransferase, alanine aminotransferase, and lactate dehydrogenase activities were determined in plasma of rats. Lipid peroxidation, protein carbonyl, and non-protein thiol levels as well as catalase, superoxide dismutase, glutathione peroxidase, glutathione reductase, and gluthatione S-transferase activities were determined in livers of rats. Hematological parameters were also determined.

Results

The results showed that CPF caused hepatic oxidative damage, as demonstrated by an increase in lipid peroxidation and protein carbonyl levels which was associated with a decrease in antioxidant defenses. CPF exposure caused a reduction in the leukocyte, indicating hematologic toxicity. (PhSe)₂ was effective in attenuating these toxic effects caused by CPF exposure in rats.

Conclusions

The results indicated that (PhSe)₂ was effective in protecting the hepatic and hematologic toxicity induced by acute CPF exposure in rats.     

Pesticide residues in Portuguese strawberries grown in 2009–2010 using integrated pest management and organic farming

Pesticides are among the most widely used chemicals in the world. Because of the widespread use of agricultural chemicals in food production, people are exposed to low levels of pesticide residues through their diets. Scientists do not yet have a total understanding of the health effects of these pesticide residues. This work aims to determine differences in terms of pesticide residue content in Portuguese strawberries grown using different agriculture practices. The Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method was conducted and shown to have good performance for multiclass pesticides extraction in strawberries. The screening of 25 pesticides residue was performed by gas chromatography?Ctandem mass spectrometry. In quantitative validation, acceptable performances were achieved with recoveries of 70?C120 and <12?% residual standard deviation for 25 pesticides. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability. The limits of detection were in the range of 0.1?C28???g/kg. The method was applied to analyze strawberry samples from organic and integrated pest management (IPM) practices harvested in 2009?C2010. The results showed the presence of fludioxonil, bifenthrin, mepanipyrim, tolylfluanid, cyprodinil, tetraconazole, and malathion when using IPM below the maximum residue levels.     

Stabilization/solidification of fly ashes and concrete production from bottom and circulating ashes produced in a power plant working under mono and co-combustion conditions

Two combustion tests were performed in a fluidized bed combustor of a thermo-electric power plant: (1) combustion of coal; (2) co-combustion of coal (68.7% w/w), sewage sludge (9.2% w/w) and meat and bone meal (MBM) (22.1% w/w). Three samples of ashes (bottom, circulating and fly ashes) were collected in each combustion test. The ashes were submitted to the following assays: (a) evaluation of the leaching behaviour; (b) stabilization/solidification of fly ashes and evaluation of the leaching behaviour of the stabilized/solidified (s/s) materials; (c) production of concrete from bottom and circulating ashes. The eluates of all materials were submitted to chemical and ecotoxicological characterizations. The crude ashes have shown similar chemical and ecotoxicological properties. The s/s materials have presented compressive strengths between 25 and 40 MPa, low emission levels of metals through leaching and were classified as non-hazardous materials. The formulations of concrete have presented compressive strengths between 12 and 24 MPa. According to the Dutch Building Materials Decree, some concrete formulations can be used in both scenarios of limited moistening and without insulation, and with permanent moistening and with insulation.     

Enhancing p-cresol extraction from soil

Soil washing is a potential technology for rapid removal of organic hydrocarbons sorbed to soils. In this work, p-cresol desorption with different non-ionic surfactants (Tween 80, Brij 30 and Triton X-100) was compared to cyclodextrine and citrate as solubilizer. A series of batch extraction experiments were conducted at 20 °C using the field soil with different extracting solutions at various concentrations to investigate the removal efficiency and to optimize the concentration of the extractant. The use of the different extracting agents was very selective to p-cresol extraction, minimizing soil organic matter releasing and maintaining the natural pH of the soil. The highest asymptotic values of desorption percentages were obtained for Tween 80 and Brij 30 at 48 h. However, Brij 30 ecotoxicity (EC₅₀ = 0.5 mg L⁻¹) is in the same order of that obtained for p-cresol, being this surfactant clearly ruled out. Liquid to solid ratio of 2.5 mL g⁻¹ presented the best extraction results, while concentrations higher than 1 g L⁻¹ for Tween 80 and Citrate did not produce any significant effect on the desorption efficiency. p-Cresol extraction efficiencies higher than 70% and 60% for Tween 80 and Citrate, respectively.     

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

Background

Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures.

Methods

Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories.

Results

Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L⁻¹, 15.56 μg L⁻¹, and 1.31 μg L⁻¹, respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking.

Conclusions

Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.     

Effects of solar radiation on the fluorescence properties and molecular weight of fulvic acids from pulp mill effluents

The pulp and paper industry generates large volume of wastewater that adversely affects water resources. Lignin derived macromolecular compounds, similar to natural humic substances, are the main waste products in the pulp mill effluents. The UV-Vis and fluorescence spectroscopies were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. Solar irradiation of the solutions of these fulvic acids caused solution acidification and decay both in the UV-Vis absorbance and in the fluorescence. This decay was not the same for the whole spectra but pointed to the selective photodegradation of lignin typical structures. Furthermore, by sequential ultrafiltration it was found that during irradiation, the high-molecular weight fractions were destroyed and low-molecular-weight constituents, potentially more able to penetrate the cell membranes of living organisms were formed. Photodegradation of macromolecular organic matter from a kraft pulp mill effluent may be a key process occurring in natural waters that modifies the physicochemical properties of such effluents.     

Cephalopods and cetaceans as indicators of offshore bioavailability of cadmium off Central South Brazil Bight

Regarding Brazilian coast, industrial and urban developments are concentrated along Central South Brazil Bight. Samples from inshore and offshore species from the concerned area were analyzed, comprising 24 cetaceans (9 species) and 32 squids (2 species). Cadmium was determined by GFAAS and our results were in agreement with certified values (DOLT-2, NRCC). Mean cadmium concentration (in microg/g, wet weight) observed in the digestive gland of sexually mature Argentine short-finned squids (Illex argentinus) was 1002.9. To our knowledge this is the highest cadmium level ever reported for a cephalopod. Concerning cetaceans, our results include one of the highest renal cadmium concentrations described for striped dolphins (71.29 microg/g, wet weight). Anthropogenic action, upwelling and cannibalism of Argentine short-finned squid on the studied area are possible reasons for such remarkable cadmium concentrations.     

CDM Projects under the Kyoto Protocol: A Methodology for Sustainability Assessment – Experiences from South Africa and Uruguay

Under the Clean Development Mechanism (CDM) of the Kyoto Protocol, industrialised countries may finance greenhouse gases mitigation projects in developing countries. The Kyoto Protocol explicitly requires that the CDM shall assist developing countries to achieve sustainable development. However, a clear definition of sustainability for CDM projects is still debatable. MATA-CDM (Multi-Attributive Assessment of CDM Projects) is an approach that facilitates a quantitative assessment of potential projects regarding their contribution to sustainable development. This paper presents applications of MATA-CDM in two different countries. In South Africa, the application was done mainly for academic and demonstrative purposes, whereas in Uruguay it was implemented together with the responsible Designated National Authority (DNA). The work in both countries included the selection of sustainability criteria and measurable indicators. Experts weighted the criteria using personal interviews and a multi-stakeholder workshop. This method was applied to three potential CDM projects in South Africa and one in Uruguay. Results show that under the conditions of this study, the MATA-CDM approach yet fails to yield a perfect quantitative overall sustainability assessment of CDM projects but that several findings could be useful to further develop the approach with the aim to translate the vague term sustainable development to a mainstream project level. Valuable experience was in particular collected with different stakeholder processes to perform criteria weighting.