A novel HS-SBSE system coupled with gas chromatography and mass spectrometry for the analysis of organochlorine pesticides in water samples

A methodology to analyze organochlorine pesticides (OCPs) in water samples has been accomplished by using headspace stir bar sorptive extraction (HS-SBSE). The bars were in house coated with a thick film of PDMS in order to properly work in the headspace mode. Sampling was done by a novel HS-SBSE system whereas the analysis was performed by capillary GC coupled mass spectrometric detection (HS-SBSE-GC-MS). The extraction optimization, using different experimental parameters has been established by a standard equilibrium time of 120 min at 85 degrees C. A mixture of ACN/toluene as back extraction solvent promoted a good performance to remove the OCPs sorbed in the bar. Reproducibility between 2.1 and 14.8% and linearity between 0.96 and 1.0 were obtained for pesticides spiked in a linear range between 5 and 17 ng/g in water samples during the bar evaluation.

Brazil in Africa: Another Emerging Power in the Continent?

This paper develops three basic arguments. First, it presents the basic underpinnings of Brazilian diplomacy in the past half century, concentrating on the changes adopted in the 1980s and the 1990s up to the foreign policy put forward by Lula`s government (2003-2009). It recognises that Lula`s foreign policy represents a step forward, especially where Africa is concerned. However, it does not seem to be clear whether the Brazilian economy has enough strength to sustain such a foreign policy, as is shown in the second part of the paper. This is indeed the case if comparisons are made with India, China and even South Africa, when the latter`s regional role is considered. Finally, an effort is made to summarise the recent political cooperation established between Brazil and African countries as well as to present an overview of Brazil`s trade and investment relations both with the region as a whole and with some important individual partners. Once this picture is established, we investigate whether these realmsdiplomatic/political and economictake independent tracks, or if they do interact in a coherent manner. Africa remained deep inside Brazil and Brazilians, not as something external to ourselves. But as a mythic space; neither geographical, nor historical.

Polychlorinated biphenyls and organochlorine pesticides in plastics ingested by seabirds

The occurrence of plastic objects in the digestive tract was assessed in eight species of Procellariiformes collected in southern Brazil and the occurrence of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the ingested plastics pellets and plastic fragments was evaluated. PCBs were detected in plastic pellets (491 ng g(-1)) and plastic fragments (243-418 ng g(-1)). Among the OCPs, p,p`-DDE had the highest concentrations, ranging from 68.0 to 99.0 ng g(-1). The occurrence of organic pollutants in post-consumer plastics supports the fact that plastics are an important source carrying persistent organic pollutants in the marine environment. Although transfer through the food chain may be the main source of exposure to POPs to seabirds, plastics could be an additional source for the organisms which ingest them, like Procellariiformes which are the seabirds most affected by plastic pollution. (c) 2010 Elsevier Ltd. All rights reserved.

Chlorinated pesticides, polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the fat tissue of seabirds from King George Island, Antarctica

Antarctic Brazilian Program (PROANTAR)

Is production the core competence for the internationalization of emerging country firms?

The rise of new multinationals in countries like Brazil provides an opportunity to revisit and carefully construct theories of how firms internationalize, a topic on which extant theory is weak. Brazilian firms are "infant multinationals", unlike developed country firms that are "mature multinationals". They are also internationalizing in a very different global context, and can do so on the basis of different competitive advantages than multinationals that came before. Therefore, this study aims at creating subsidies for theory building about early-stage internationalization. Emerging country firms have Production competences as main competitive asset to internationalize, what reflects their competitive positioning in home markets and their entry strategy in international markets. In the case of early-entrants - Western multinationals in the 1950s and Japanese in the 1980s - the Production competence played a key role for successful internationalization. Thus, the focus of the study is the role that the Production competence plays in the internationalization of late-entrants, the emerging country multinationals. The research design considers not only the position of the headquarters but also the initiatives of the subsidiaries and the dynamic interplay between both. The paper allows a better understanding of internationalization processes and the role of Production, when firms start building their own international networks. It brings relevant insights about the paths that are being followed by emerging country multinationals, the difficulties they find, the solutions they develop. These are important inputs not only for new theory building but also for managerial practice. (C) 2012 Elsevier B.V. All rights reserved.

Contamination by chlorinated pesticides, PCBs and PBDEs in Atlantic spotted dolphin (Stenella frontalis) in western South Atlantic

Chlorinated pesticides, PCBs and PBDEs were analysed in nine blubber samples of Atlantic spotted dolphins, Stenella frontalis, incidentally captured during fishing operations in southern and southeastern Brazil between 2005 and 2007. The majority of compounds analysed were detected, suggesting widespread contamination over the region. Although the samples came from a location far from main coastal industrial areas, the results revealed an influence from such sources. Therefore, levels of PCBs (774-23659 ng g(-1) lipid wt.) and PBDEs (23-1326 ng g(-1) lipid wt.) detected seem to be related to the movement of individuals throughout near-shore and offshore waters. The sample from a lactating female exhibited a lower level of contamination and a distinct pattern, indicating selective transfer favouring less lipophilic compounds.

PCBs, PBDEs and organochlorine pesticides in crabs Hepatus pudibundus and Callinectes danae from Santos Bay, State of Sao Paulo, Brazil

The occurrence of persistent organic pollutants (POPS) as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDE) in crabs Hepatus pudibundus and Callinectes danae was assessed from two different places inside of the Santos Bay and Moela Island near one of the most economically important metropolitan areas in Southern Brazil. Among POPs analyzed, Sigma PCBs (222-923 ng g(-1) lipid weight) and Sigma DDTs (154-410 ng g(-1) lw) exhibited the highest concentrations in the crabs. Sigma HCHs ranged from 10.3 to 30.9 ng g(-1), lw and were found in all individuals. Other OCPs found in lower concentration was Mirex (7.6-41.6 ng g(-1) lw) and HCB (5.83-16.9 ng g(-1) lw). Sigma PBDEs (24.1 ng g(-1) lw) were only found in one male individual from the species C. danae collected near to the submarine sewage of Santos. Male crabs showed higher POP concentrations than female crabs for those two species. (C) 2011 Elsevier Ltd. All rights reserved.

Institutional arrangements in the emerging biodiesel industry: Case studies from Minas Gerais-Brazil

Connecting (small) family farmers to the emerging biodiesel industry requires careful design of the institutional arrangements between the producers of oil crops and the processing companies. According to institutional economics theory, the design of effective and efficient arrangements depends on production and transaction characteristics, the institutional environment, and the organizational environment supporting the transaction between producers and the industry. This paper presents a comparative study on two cases in the feedstock-for-biodiesel industry in the state of Minas Gerais, Brazil. The two case studies represent the production and transaction system of soybeans (Glycine max L Merrill) and castor beans (Ricinus communis L). Important elements of effective and efficient institutional arrangements are farmer collective action, availability of technical and financial support, and farmer experience with particular crops. (C) 2011 Elsevier Ltd. All rights reserved.

An integrated approach to evaluate emerging contaminants in drinking water

The chemical stock of emerging contaminants in Brazilian drinking water is of great interest due to the poor water quality at surface water intakes. In addition, little is known about the effect of some contaminants, such as endocrine disrupting chemicals (EDCs), which may be present in both raw and treated water. The aim of this work was to evaluate selected emerging contaminants in Brazilian waters using both chemical and biological analyses. Sampling sites were established in different municipalities based upon raw water quality data. Estrone, 17 beta-estradiol, estriol, 17 alpha-ethinylestradiol, bisphenol A, 4-n-octylphenol and 4-n-nonylphenol were determined in the samples by liquid chromatography-tandem mass spectrometry. A yeast assay using a Saccharomyces cerevisiae bioluminescent bioreporter was used to evaluate the estrogenic activity of the water samples. The first integrated results revealed similarities between the two individual approaches, since higher values for the bioassay were accompanied by significant concentrations of some selected compounds in surface water samples. No estrogenicity was observed for drinking water samples. Our results also indicate that the usual paradigm of evaluating water quality by measuring selected EDCs in a given water sample via chemical analysis, needs to be reviewed since the observed estrogenicity of a water sample is now a better guiding parameter to the selection of samples and substances to be chemically investigated in further analysis. So far, the data bank produced in this work, i.e., the comparison between chemical burden and observed estrogenicity, is not yet sufficiently robust to fully guide this decision. (C) 2011 Elsevier B.V. All rights reserved.

Development of methodology for determination of pesticides residue in water by SPE/HPLC/DAD

To boost crop yield, sugarcane growers are using increasing amounts of pesticides to combat insects and weeds. But residues of these compounds can pollute water resources, such as lakes, rivers and aquifers. The present paper reports the results of a study of water samples from the Feijao River, which is the source of drinking water for the city of Sao Carlos, Sao Paulo, Brazil. The samples were evaluated for the presence of four leading pesticides - ametryn, atrazine, diuron and fipronil - used on sugarcane, the dominant culture in the region. The samples were obtained from three points along the river: the headwaters, along the middle course of the river and just before the municipal water intake station. The pesticides were extracted from the water samples by solid-phase extraction (SPE) and then analyzed by liquid chromatography with diode array detection (LC-DAD). The analytical method was validated by traditional methods, obtaining recovery values between 90 and 95%, with precision deviations inferior to 2.56%, correlation coefficients above 0.99 and detection and quantification limits varying from 0.02 to 0.05 mg L-1 and 0.07 to 0.17 mg L-1, respectively. No presence of residues of the pesticides was detected in the samples, considering the detection limits of the method employed.

Surface-enhanced Raman spectroscopy studies of organophosphorous model molecules and pesticides

This work reports the analytical application of surface-enhanced Raman spectroscopy (SERS) in the trace analysis of organophosphorous pesticides (trichlorfon and glyphosate) and model organophosphorous compounds (dimethyl methylphosphonate and o-ethyl methylphosphonothioate) bearing different functional groups. SERS measurements were carried out using Ag nanocubes with an edge square dimension of ca. 100 nm as substrates. Density functional theory (DFT) with the B3LYP functional was used for the optimization of ground state geometries and simulation of Raman spectra of the organophosphorous compounds and their silver complexes. Adsorption geometries and marker bands were identified for each of the investigated compound. Results indicate the usefulness of SERS methodology for the sensitive analyses of organophosphorous compounds through the use of vibrational spectroscopy.

TOWARDS NEW BOTANICAL PESTICIDES: THE TOXIC EFFECT OF Eremanthus goyazensis (Asteraceae) LEAVES ESSENTIAL OIL AGAINST Brevipalpus phoenicis (Acari: Tenuipalpidae)

This work reports the chemical characterization of Eremanthus goyzensis essential oil and its toxic effect over Brevipalpus phoenicis. The essential oil displayed a major composition of sesquiterpenes (61.87%) including trans-caryophillene (26.81%) and germacrene-D (13.31%). The fumigation test indicated a promising bioactivity over adult B. phoenicis individuals at 24 h (2.03 mu L/L of air) and 48 h (1.08 mu L/L of air) of exposition. A brief discussion of essential oils composition and their singular role on the toxic effect over B. phoenicis is provided here. Our results may contribute to a new and profitable use of a species of Brazilian flora on agribusiness.

IINTERNATIONAL STRATEGY FOR AN EMERGING MULTINATIONAL IN BRAZIL: THE CASE OF JBS

The focus of this study is on questioning whether the traditional theories of internationalization are adequate to explain the international expansion of multinationals from emerging countries. Looking forward on this issue, we investigate the internationalization strategies adopted by JBS, a Brazilian multinational of the beef industry. The results show that the company adopted two of the five generic strategies specific to the context of emerging countries suggested by Ramamurti and Singh (2009): global consolidator and vertical integrator. Moreover, when analyzing the internationalization of the company under study, the speed of the process is highlighted when compared to traditional multinationals. It is concluded that the main mode of entry that allowed the international expansion was the acquisition and that this strategy has advantages to the company, such as access to strategic resources and rapid growth, possibly overcoming the liability of foreignness, the opportunity to compete globally and the diversification of segments that generate synergies to the company's activities.

Electrochemical detection of carbamate pesticides in fruit and vegetables with a biosensor based on acetylcholinesterase immobilised on a composite of polyaniline-carbon nanotubes

A sensitive electrochemical acetylcholinesterase (AChE) biosensor was successfully developed on polyaniline (PANI) and multi-walled carbon nanotubes (MWCNTs) core-shell modified glassy carbon electrode (GC), and used to detect carbamate pesticides in fruit and vegetables (apple, broccoli and cabbage). The pesticide biosensors were applied in the detection of carbaryl and methomyl pesticides in food samples using chronoamperometry (CA). The GC/MWCNT/PANI/AChE biosensor exhibited detection limits of 1.4 and 0.95 mu mol L-1, respectively, for carbaryl and methomyl. These detection limits were below the allowable concentrations set by Brazilian regulation standards for the samples in which these pesticides were analysed. Reproducibility and repeatability values of 2.6% and 3.2%, respectively, were obtained in the conventional procedure. The proposed biosensor was successfully applied in the determination of carbamate pesticides in cabbage, broccoli and apple samples without any spiking procedure. The obtained results were in full agreement with those from the HPLC procedure. (C) 2012 Elsevier Ltd. All rights reserved.

Integrated ecological risk assessment of pesticides in tropical ecosystems: A case study with carbofuran in Brazil

The aim of the present study is to contribute an ecologically relevant assessment of the ecotoxicological effects of pesticide applications in agricultural areas in the tropics, using an integrated approach with information gathered from soil and aquatic compartments. Carbofuran, an insecticide/nematicide used widely on sugarcane crops, was selected as a model substance. To evaluate the toxic effects of pesticide spraying for soil biota, as well as the potential indirect effects on aquatic biota resulting from surface runoff and/or leaching, field and laboratory (using a cost-effective simulator of pesticide applications) trials were performed. Standard ecotoxicological tests were performed with soil (Eisenia andrei, Folsomia candida, and Enchytraeus crypticus) and aquatic (Ceriodaphnia silvestrii) organisms, using serial dilutions of soil, eluate, leachate, and runoff samples. Among soil organisms, sensitivity was found to be E. crypticus < E. andrei < F. candida. Among the aqueous extracts, mortality of C. silvestrii was extreme in runoff samples, whereas eluates were by far the least toxic samples. A generally higher toxicity was found in the bioassays performed with samples from the field trial, indicating the need for improvements in the laboratory simulator. However, the tool developed proved to be valuable in evaluating the toxic effects of pesticide spraying in soils and the potential risks for aquatic compartments. Environ. Toxicol. Chem. 2012;31:437-445. (C) 2011 SETAC