Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.     

Spectrophotometric determination of the fungicide captan

A spectrophotometric method for the determination of the fungicide captan has been developed based on its reaction with thiosemicarbazide. The absorbance was measured at 315 nm. The effects of the proportion of water, thiosemicarbazide concentration, pH and temperature on this reaction was studied to select the best chemical conditions. The calibration graph was obtained between 1.2 and 30 ppm and the detection limit is 0.5 ppm. The RSD (n = 10) was 1.34%. Possible interference of various pesticides was examined. The method was applied to the determination of captan in agrochemical formulations. Results agree well with the labelled values and also with results that were obtained by a polarographic method.     

Comparative study on the susceptibility of freshwater species to copper-based pesticides

Copper compounds have been intentionally introduced into water bodies as aquatic plant herbicides, algicides and molluscicides. Copper-based fertilizers and fungicides have been widely used in agriculture as well. Despite the fact that copper is an essential element for all biota, elevated concentrations of this metal have been shown to affect a variety of aquatic organisms. Nonetheless, comparative studies on the susceptibility of different freshwater species to copper compounds have seldom been performed. This study was conducted to compare toxicity of copper-based pesticides (copper oxychloride, cuprous oxide and copper sulfate) to different freshwater target (Raphidocelis subcapitata, a planktonic alga and Biomphalaria glabrata, a snail) and non-target (Daphnia similis, a planktonic crustacean and Danio rerio, a fish) organisms. Test water parameters were as follows: pH = 7.4 +/- 0.1; hardness 44 +/- 1 mg/l as CaCO3; DO 8-9 mg/l at the beginning and > 4 mg/l at the end; temperature, fish and snails 25 +/- 1 degrees C, Daphnia 20 +/- 2 degrees C, algae 24 +/- 1 degrees C. D. similis (immobilization), 48-h EC50s (95% CLs) ranging from 0.013 (0.011-0.016) to 0.043 (0.033-0.057) mg Cu/l, and R. subcapitata (growth inhibition), 96-h IC50s from 0.071 (0.045-0.099) to 0.137 (0.090-0.174) mg Cu/l, were the most susceptible species. B. glabrata (lethality), 48-h LC50s from 0.179 (0.102-0.270) to 0.854 (0.553-1.457) mg Cu/l, and D. rerio (lethality), 48-h LC50s 0.063 (0.045-0.089), 0.192 (0.133-0.272) and 0.714 (0.494-1.016) mg Cu/l, were less susceptible than Daphnia to copper-based pesticides. Findings from the present study therefore suggest that increased levels of copper in water bodies is likely to adversely affect a variety of aquatic species.     

The influence of axle position and the use of accessories on the activity of upper limb muscles during manual wheelchair propulsion

Introduction. Wheelchair configuration is an important factor influencing the ergonomics of the user–device interface and, from a biomechanical point of view, small changes in chair setup may have a positive influence on the demand on the upper limbs during manual propulsion. This study aimed to investigate the influence of the position of the rear wheels’ axle and the use of accessories on the activity of upper limb muscles during manual wheelchair propulsion. Methods. Electromyography signals of the biceps, triceps, anterior deltoids and pectoralis major were collected for 11 able-bodied subjects in a wheelchair propulsion protocol with four different wheelchair configurations (differing in axle position and the use of accessories) on a straightforward sprint and a slalom course. Results. With accessories, moving the axle forward led to a decrease in the activity of all muscles in both the straightforward sprint (significant differences in triceps, anterior deltoids and biceps) and the slalom course (significant difference in anterior deltoids and biceps). However, when propelling the chair without accessories, no difference was found related to axle position. Conclusion. Changes in wheelchair configuration can influence the ergonomics of manual wheelchair propulsion. Reducing the biomechanical loads may benefit users’ mobility, independence and social participation.     

Interactions Between Spatially Explicit Conservation and Management Measures: Implications for the Governance of Marine Protected Areas

Marine protected areas are not established in an institutional and governance vacuum and managers should pay attention to the wider social–ecological system in which they are immersed. This article examines Islas Choros-Damas Marine Reserve, a small marine protected area located in a highly productive and biologically diverse coastal marine ecosystem in northern Chile, and the interactions between human, institutional, and ecological dimensions beyond those existing within its boundaries. Through documents analysis, surveys, and interviews, we described marine reserve implementation (governing system) and the social and natural ecosystem-to-be-governed. We analyzed the interactions and the connections between the marine reserve and other spatially explicit conservation and/or management measures existing in the area and influencing management outcomes and governance. A top-down approach with poor stakeholder involvement characterized the implementation process. The marine reserve is highly connected with other spatially explicit measures and with a wider social–ecological system through various ecological processes and socio-economic interactions. Current institutional interactions with positive effects on the management and governance are scarce, although several potential interactions may be developed. For the study area, any management action must recognize interferences from outside conditions and consider some of them (e.g., ecotourism management) as cross-cutting actions for the entire social–ecological system. We consider that institutional interactions and the development of social networks are opportunities to any collective effort aiming to improve governance of Islas Choros-Damas marine reserve. Communication of connections and interactions between marine protected areas and the wider social–ecological system (as described in this study) is proposed as a strategy to improve stakeholder participation in Chilean marine protected areas.     

Impacts of changes in land use and fragmentation patterns on Atlantic coastal forests in northern Spain

Changes in forested landscapes may have important consequences for ecosystem services and biodiversity conservation. In northern Spain, major changes in land use occurred during the second half of the 20th century, but their impacts on forests have not been quantified. We evaluated the dynamics of landscape and forest distribution patterns between 1957 and 2003 in Fragas do Eume Natural Park (northwestern Spain). We used orthoimages and a set of standard landscape metrics to determine transitions between land cover classes and to examine forest distribution patterns. Eucalypt plantations showed the greatest increase in area (197%) over time. Furthermore, transitions to eucalypt plantations were found in all major land cover classes. Forest showed a net decline of 20% in total area and represented 30% of the landscape area in 2003. Forest losses were mainly due to eucalypt plantations and the building of a water reservoir, while forest gains were due to increases in shrubland, meadows and cultivated fields which had been recolonised. Forest patch size and core area decreased, and edge length increased over time. In turn, increases were obtained in mean distance between forest patches, and in adjacency to eucalypt plantations and to a water reservoir. These results suggest an increase in forest fragmentation from 1957 to 2003, as well as a change in the nature of the habitat surrounding forest patches. This study shows that land use changes, mostly from eucalypt plantation intensification, negatively affected forested habitats, although some regeneration was ongoing through ecological succession from land abandonment.     

Effect of delayed first feeding on larval performance of the spider crab Maja brachydactyla assessed by digestive enzyme activities and biometric parameters

The effect of food deprivation on larval performance of the spider crab Maja brachydactyla was studied in terms of survival, moulting capacity, size, weight and enzymatic activities. Five feeding treatments that differed in the initial age of first feeding larvae (fed from hatching, 2, 4 and 6 days post-hatching and unfed) were tested for 20 days. Newly hatched larvae kept without food supply lasted for 10 days and did not moult; with 50% survival observed at 6 days post-hatching. Larvae (zoea I stage) were only able to tolerate 2 days of food deprivation after the onset of exogenous feeding without their performance being compromised. Multivariate analyses suggest that digestive enzyme activities may be good indicators of the nutritional condition of larvae.     

Are local extinctions and recolonizations continuing at the colder limits of marine fish distributions? Halobatrachus didactylus (Bloch & Schneider, 1801), a possible candidate

In this paper, we compare the populations of the Lusitanian toadfish Halobatrachus didactylus along the Portuguese shore, using a putative fragment of the mitochondrial control region and the first intron of the S7 ribosomal protein gene. This demersal species ranges from the tropical West African coast to the Iberian Peninsula and the Mediterranean, having its northern limit in the Tagus River. For the putative control region, a single haplotype occurs in all fish from Tagus and Sado (the location immediately to the south) with a clear increase in diversity to the South, peaking at Algarve (south Portugal). The data seem to point to a very recent Holocenic colonization of Tagus and Sado from the South (possibly Algarve). We suggest that even small oscillations in sea surface temperature (SST) may cause local extinctions and subsequent recolonizations in populations of thermophilic fish that are at the cold limit of their distributions.