Solubilities of selected organic electronic materials in pressurized hot water and estimations of aqueous solubilities at 298.15 K

Increasing production and disposal of organic light-emitting diode (OLED) displays for smartphones and tablets may have impact on the environment depending on the aqueous solubility of the pertinent chemicals. Here, aqueous solubilities are presented for several compounds, mostly aromatic amines, used as hole transport materials in the OLED displays. Solute selection includes 1,4-bis(diphenylamino)benzene, tetra-N-phenylbenzidine, 4,4′-bis(N-carbazolyl)-1,1′-biphenyl, 1,3,5-tris(diphenylamino)benzene, and 9,10-bis(phenylethynyl)anthracene. The solubilities are those in pressurized hot water (PHW), i.e., measured at elevated temperature (up to 260 °C) and pressure. The semi-quantitative estimates of room-temperature solubilities of the solutes have been obtained from extrapolations of the solubilities in PHW. For the compounds studied, the estimated aqueous solubilities at room temperature do not exceed 2 × 10^?11 g of the solute per 1 kg of water. Aqueous solubilities of triphenylamine have also been measured and used to upgrade a recent group-contribution model of aqueous solubilities of organic nonelectrolytes with the parameters for the nitrogen atom in aromatic amines.     

Impact of long‐term pesticide applications on some soil biological parameters

Abstract

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (São Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)‐activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron‐oxide reduction, and the microbial biomass was estimated by the substrate (glucose)‐indiced respiration. Increases in DHA‐activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron‐reduction. In the experimental field soil, the increases in DHA‐activity were followed only by decreases in iron‐reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

Ecosystem services and hydroelectricity in Central America: modelling service flows with fuzzy logic and expert knowledge

Because ecosystem services are generally not produced and used in the same place, their assessment should consider the flows of services from ecosystems to users. These flows depend on the characteristics and spatial distribution of ecosystems and users, the spatial relationships between them, and the presence of filters or barriers between ecosystems and users. The objective of this paper is to map the ecosystem services provided to the Costa Rican and Nicaraguan hydroelectric sectors, which are crucial sectors for national sustainable development and depend directly on hydrological ecosystem services. The paper presents an approach for modelling the flows of multiple services from diverse ecosystems to diverse users through different kinds of filters in a landscape. The approach uses expert knowledge and fuzzy numbers to handle uncertainties. The analyses for Costa Rica and Nicaragua show how the approach helps identify priority areas for the conservation and restoration of forests for the services they provide to the hydroelectric sector. As such, it is a useful tool for defining spatially targeted policies for the conservation of ecosystem services and for involving the users of ecosystem services in ecosystem management.     

Sensitivity of Portuguese forest fires to climatic, human, and landscape variables: subnational differences between fire drivers in extreme fire years and decadal averages

Within the changing fire regimes of Portugal, the relative importance of humans and climatic variability for regional fire statistics remains poorly understood. This work investigates the statistical relationship between temporal dynamics of fire events in Portugal and a set of socioeconomic, landscape, and climatic variables for the time periods of 1980–1990, 1991–2000, and extreme fires years. For 10 of 15 districts, it was possible to observe moderate shifts in the significance of fire drivers for the first two decadal periods. For others, pronounced changes of the significance of fire drivers were found across time. Results point toward a dynamic (perhaps highly non-linear) behavior of socioeconomic and landscape fire drivers, especially during the occurrence of extreme fire years of 2003 and 2005. At country level, population density alone explained 42% of the inter-annual and inter-district deviance in number of fires. At the same temporal and spatial scale, the explanatory power of temperature anomalies proved to explain 43% of area burnt. We highlight the necessity of including a broad set of socioeconomic and landscape fire drivers in order to account for potential significance shifts. In addition, although climate does trigger broad favorable fire conditions across Portugal mainland, socioeconomic and landscape factors proved to determine much of the complex fire patterns at a subnational scale.     

Land-cover changes in and around a National Park in a mountain landscape in the Pyrenees

The current state of Mediterranean mountain areas has been driven by two main factors: intense traditional human activity and the dynamics of the ecosystem itself. In this study, we examine land-cover changes in a National Park in the Pyrenees mountains (NE Iberian Peninsula), which was designated a protected area 55 years ago. First, we have analyzed spatio-temporal changes in land-cover pattern and forest dynamics from 1957 to 2005. During this period, land-cover dynamics consisted of two main processes: (i) expansion of the forest area and (ii) increasing cover of forests already present in 1957. To analyze the role of the conservation level of the park, we have also compared the results obtained within the park with those of unprotected, peripheral areas. In the two areas with different protection level, dense forests increased throughout the period because of the reduction in forestry activities. The peripheral area showed a higher rate of forest-cover change from 1957 to 2005 compared to the National Park. This higher increase in forest cover in the peripheral area could be related to a higher proportion in the National Park of screes and rocky areas and to the decline and transformation of forest activities in these peripheral, lower elevation areas.     

Biochemical biomarkers in Nile tilapia (Oreochromis niloticus) after short-term exposure to diesel oil, pure biodiesel and biodiesel blends

Fossil fuels such as diesel are being gradually replaced by biodiesel, a renewable energy source, cheaper and less polluting. However, little is known about the toxic effects of this new energy source on aquatic organisms. Thus, we evaluated biochemical biomarkers related to oxidative stress in Nile tilapia (Oreochromis niloticus) after two and seven exposure days to diesel and pure biodiesel (B100) and blends B5 and B20 at concentrations of 0.01 and 0.1 mL L⁻¹. The hepatic ethoxyresorufin-O-deethylase activity was highly induced in all groups, except for those animals exposed to B100. There was an increase in lipid peroxidation in liver and gills in the group exposed to the higher concentration of B5. All treatments caused a significant increase in the levels of 1-hydroxypyrene excreted in the bile after 2 and 7 d, except for those fish exposed to B100. The hepatic glutathione-S-transferase increased after 7 d in animals exposed to the higher concentration of diesel and in the gill of fish exposed to the higher concentration of pure diesel and B5, but decreased for the two tested concentrations of B100. Superoxide dismutase, catalase and glutathione peroxidase also presented significant changes according to the treatments for all groups, including B100. Biodiesel B20 in the conditions tested had fewer adverse effects than diesel and B5 for the Nile tilapia, and can be suggested as a less harmful fuel in substitution to diesel. However, even B100 could activate biochemical responses in fish, at the experimental conditions tested, indicating that this fuel can also represent a risk to the aquatic biota.     

Dietary uptake of polybrominated diphenyl ethers (PBDEs), occurrence and profiles, in aquacultured turbots (Psetta maxima) from Galicia, Spain

Polybromodiphenyl ethers (PBDEs) are one of the many toxic chemicals present in the environment and in the food we eat every day, being fish one of the main sources of persistent organic pollutants in our diet; like other lipid-related contaminants, they are of concern since they can bioaccumulate and biomagnify through the trophic chain. We published a study focused on the dietary uptake of dioxins and furans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) in a set of samples of Spanish farmed turbot (Blanco et al., 2007). In the present paper, we extend the study to PBDEs to provide more information about the uptake and transfer from feed to fish of halogenated contaminants. PBDEs in the feeds (2.35-4.76 ng g(-1)) were reflected in turbot fillets (0.54-2.05 ng g(-1)): predominant congeners were tetra-BDE 47, penta-BDEs 99 and 100. It is remarkable that tetra-BDE 49, accounting for only 2% in the feed, contributed to 15% of total PBDEs in turbot fillets. Dietary net accumulation values, 30-45%, showed that tri-, tetra-, penta- and hexa-BDEs were as efficiently transferred into turbot as dl-PCBs and tetra- and penta-chlorinated PCDD/Fs. Lipid-normalized biomagnification factors relating concentration in fish and in feed, BMFs>1 were obtained, except for BDE 209. BDE 49 accumulation, 90%, was possibly contributed by metabolism of higher brominated BDEs. Implication in aquaculture management is a need for uncontaminated fish feed to offer safe products.     

The influence of metal speciation on the bioavailability and sub-cellular distribution of cadmium to the terrestrial isopod, Porcellio dilatatus

Cadmium is a non-essential toxic metal that is able to bioaccumulate in both flora fauna and has the potential to biomagnify in some food chains. However, the form in which cadmium is presented to consumers can alter the bioavailability and possibly the internal distribution of assimilated Cd. Previous studies in our laboratory highlighted differences in Cd assimilation among isopods when they were provided with a plant-based food with either Cd biologically incorporated into plant tissue or superficially amended with ionic Cd(2+). Cd is known for its high affinity for sulphur ligands in cysteine residues which form the basis for metal-binding proteins such as metallothionein. This study compares Cd assimilation efficiency (AE) in Porcellio dilatatus fed with food amended with either cadmium cysteinate or cadmium nitrate in an examination of the influence of Cd speciation on metal bioavailability followed by an examination of the sub-cellular distribution using a centrifugal fractionation protocol. As hypothesized the AE of Cd among isopods fed with Cd(NO(3))(2) (64%, SE=5%) was higher than AE for isopods fed with Cd(Cys)(2) (20%, SE=3%). The sub-cellular distribution also depended on the Cd species provided. Those isopods fed Cd(Cys)(2) allocated significantly more Cd to the cell debris and organelles fractions at the expense of allocation to metal-rich granules (MRG). The significance of the difference in sub-cellular distribution with regard to toxicity is discussed. This paper demonstrates that the assimilation and internal detoxification of Cd is dependent on the chemical form of Cd presented to the isopod.     

Applicability of microwave-assisted extraction combined with LC-MS/MS in the evaluation of booster biocide levels in harbour sediments

A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography-tandem mass spectrometry (LC-MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE-SPE). The effects of different variables on MAE-SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3 ng g⁻¹. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain).