Polyurethanes Based on Atactic Poly[(R,S)-3-hydroxybutyrate]: Preliminary Degradation Studies in Simulated Body Fluids

The aliphatic polyurethanes based on atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) and commercial oligomerols: poly(ε-caprolactone)diol and polyoxytetramethylenediol were investigated. a-PHB was obtained by anionic ring-opening polymerization of (R,S)-β-butyrolactone. The 4,4′-methylenedicyclohexyl diisocyanate and 1,4-butanediol were used as contributors of hard segments. The aim of the study was to determine the influence of synthetic, atactic a-PHB in soft segments of polyurethanes on their degradability in simulated body fluids (SBF) and Ringer solution. The incubation of polymer samples in both degradative solutions was carried out for 36 weeks. It was concluded that the presence of a-PHB in polyurethane structure accelerated their degradation in SBF and in Ringer solution and, protected the calcification process.     

Salt marsh plants as key mediators on the level of cadmium impact on microbial denitrification

The fate of excess nitrogen in estuaries is determined by the microbial-driven nitrogen cycle, being denitrification a key process since it definitely removes fixed nitrogen as N₂. However, estuaries receive and retain metals, which may negatively affect this process efficiency. In this study, we evaluated the role of salt marsh plants in mediating cadmium (Cd) impact on microbial denitrification process. Juncus maritimus and Phragmites australis from an estuary were collected together with the sediment involving their roots, each placed in vessels and maintained in a greenhouse, exposed to natural light, with tides simulation. Similar non-vegetated sediment vessels were prepared. After 3 weeks of accommodation, nine vessels (three per plant species plus three non-vegetated) were doped with 20 mg/L Cd²⁺ saline solution, nine vessels were doped with 2 mg/L Cd²⁺ saline solution and nine vessels were left undoped. After 10 weeks, vessels were dissembled and denitrification potential was measured in sediment slurries. Results revealed that the addition of Cd did not cause an effect on the denitrification process in non-vegetated sediment but had a clear stimulation in colonized ones (39 % for P. australis and 36 % for J. maritimus). In addition, this increase on denitrification rates was followed by a decrease on N₂O emissions and on N₂O/N₂ ratios in both J. maritimus and P. australis sediments, increasing the efficiency of the N₂O step of denitrification pathway. Therefore, our results suggested that the presence of salt marsh plants functioned as key mediators on the degree of Cd impact on microbial denitrification.     

Efficacy of new mass-trapping devices against Bactrocera oleae (Diptera tephritidae) for minimizing pesticide input in agroecosystems

Decreasing pesticide use in olive groves is central to controlling pathogens and pests such as Bactrocera oleae. This has led to the development of mass trapping devices which not only minimize pesticide use but, with improved efficacy of attractants, also decrease costs associated with pest control and ensures that the quality of olive oil is safe for human consumption. This study was undertaken to test a new device which utilizes reduced quantities of both insecticide (lambda-cyalothrin) as well as the female olive fly pheromone (1,7-dioxaspiro-(5.5)-undecane). The new device was tested against an older device manufactured by the same company. The use of plastic polymers as substrate for encapsulating the pheromone allowed for a slower pheromone release, prolonging the efficacy and duration and thus reducing costs. The density of adult populations was monitored using yellow chromotropic traps that were checked every ten days and the degree of olive infestation, as determined by preimago stages, was assessed by analyzing 100 drupes per plot. Infestation analyses were performed every ten days. The control plot had the lowest density of adults and the highest drupe infestation rate. The new devices were more effective than the older devices in both attracting adults and controlling infestation of drupes. Moreover, the new devices containing reduced amounts of pheromone and insecticide were cheaper and exhibited longer functional efficacy. In addition to the slower release of attractants, the plastic polymers used in these newer devices were also more resistant to mechanical and weather degradations. Results demonstrate that mass trapping can indeed be an effective means of controlling B. oleae via eco-sustainable olive farming.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.     

Assessment of exposure to DDT and metabolites after indoor residual spraying through the analysis of thatch material from rural African dwellings

Introduction  

We report on the analysis of 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and its metabolites in thatch and branch samples constituting the wall materials of dwellings from South African subtropical areas. This approach was used to assess the exposure to DDT in the residents of the dwellings after indoor residual spraying (IRS) following recommended sanitation practices against malaria vectors.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

Cesium-137 contamination of oak (Quercus petrae Liebl.) from sub-mediterranean zone in South Bulgaria

This study focuses on the cesium-137 (¹³⁷Cs) contamination in grass and in different compartments of oak trees growing in ecosystems, located in the zone with sub-mediterranean climate in South Bulgaria, characterized with high summer temperatures, low precipitation and often periods of drought. In 2008, three experimental sites - PP1, PP2, PP3 - were sampled in oak ecosystems from Maleshevska Mountain at 900 m above sea level. Samples from grass species and oak tree leaves, branches with different diameter, wood disks and bark were analyzed for ¹³⁷Cs activity with γ-spectrometry. The soil-to-plant transfer factor (TF) values for ¹³⁷Cs were estimated differentiating different tree compartments. Our findings showed relatively high activity concentrations of ¹³⁷Cs in oak trees even 22 years after the Chernobyl accident. The grass under oak was less contaminated compared with the oak trees. The different organs of oak trees could be distinguished according to the ¹³⁷Cs contamination as follows: bark > branches (d < 1 cm) > leaves > branches (d > 3 cm) > wood. The relatively higher contamination of bark compared with the new-formed biomass suggested that a significant part of ¹³⁷Cs was accumulated as a result of direct adsorption at the time of the main contamination event. The TF values obtained and the presence of ¹³⁷Cs in the branches, leaves and in the wood formed after 1986 confirmed that 22 years after the contamination, the main mechanism of ¹³⁷Cs entrance in tree biomass was the root uptake.     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.     

Detection of human-induced environmental disturbances in a show cave

Purpose  

We investigated the effects of human-induced disruption in a subterranean stable environment containing valuable Palaeolithic paintings and engravings (Ardales Cave, Southern Spain) using a double analytical approach.     

Comparision of the waterborne and dietary routes of exposure on the effects of Benzo(a)pyrene on biotransformation pathways in Nile tilapia (Oreochromis niloticus)

BaP is one of the most studied PAH, due to its ubiquitous presence in aquatic environments and toxicity to aquatic organisms. The main goal of this study was to assess BaP effects in Nile Tilapia after waterborne and dietary exposures, through the evaluation of EROD and GST activities in liver, gills and intestine, and BaP metabolites in bile; and also to evaluate the usefulness of these commonly used biomarkers after two different routes of exposure. Waterborne exposure to BaP led to a significant induction of EROD in all tissues analyzed (644%, 1640% and 2880% in relation to solvent in liver, gill and intestine respectively) while in dietary exposures EROD was induced only in intestine (3143%) after exposure to high BaP concentrations. GST activities with CDNB were slightly induced in liver (40%) and in gill (66%) after water exposure to BaP, and in intestine after dietary exposure to low BaP concentrations (182%). BaP metabolites in bile increased after both exposure routes, and were highly correlated with EROD activity after water exposure. In summary, this work has shown that the effects of BaP on biotransformation pathways depend on the route of exposure. Moreover, barrier tissues like gills and intestine also have an important role in the first-pass metabolism of BaP, reducing the amount of parent compound that reaches the liver to be metabolized. For that reason, EROD activity as a biomarker of exposure should also be applied in extrahepatic organs, like gills and intestine, in monitoring studies. Biliary BaP type metabolites are good reflectors of contamination levels under both exposure routes, while GST activity with CDNB as substrate, as a phase II enzyme, does not seem a reliable biomarker of exposure to BaP regardless the route of exposure.