Photodegradation of hydroxylated N-heteroaromatic derivatives in natural-like aquatic environments. A review of kinetic data of pesticide model compounds

In the present review, the results published by our group and others related with the study of the kinetic behavior and, in some cases, the mechanism of the dye-promoted photooxygenation of several hydroxypyridines, hydroxyquinolines and hydroxypyrimidines--some of them with the basic molecular structures of known pesticides, and of a few non-hydroxylated model compounds, are compiled and discussed. The main aim was to examine the experimental conditions that maximize the photodegradation efficiencies of all these compounds, under dye-sensitized photooxidation conditions similar to those frequently found in nature, with a natural dye sensitizer such as riboflavin (vitamin B2), a pigment habitually present in natural waters. The usual mechanism of action of this compound is rather complex, in many cases with the concurrent involvement of the oxidative species singlet molecular oxygen (O2(1Deltag)) and superoxide radical anion. In order to simplify the study of the processes, the results found using the synthetic dye Rose Bengal (RB), a sensitizer that generates O2(1Deltag) with high efficiency, are also discussed. RB and similar O2(1Deltag)-generators could be used for the efficient non-natural photodegradation of related pesticides in aqueous solutions under controlled conditions.     

Methane oxidation in a landfill cover with capillary barrier

The methane oxidation potential of a landfill cover with capillary barrier was investigated in an experimental plant (4.8 m x 0.8 m x 2.1m). The cover soil consisted of two layers, a mixture of compost plus sand (0.3 m) over a layer of loamy sand (0.9 m). Four different climatic conditions (summer, winter, spring and fall) were simulated. In and outgoing fluxes were measured. Gas composition, temperature, humidity, matrix potential and gas pressure were monitored in two profiles. CH4 oxidation rate within the investigated top cover ranged from 98% to 57%. The minimum was observed for a short time after irrigation. Temperature distribution, gas concentration profiles and lab-scaled batch experiments indicate that before irrigation the highest oxidising activity took place in a depth of about 30 cm. After irrigation the oxidising horizon seemed to migrate upwards since methanotrophic bacteria develop better there due to an adequate supply with oxygen. It can be assumed that the absence of oxygen is one of the most important limiting factors for the CH4 oxidation process. Abrupt cross-overs between horizons of different soil material may lead to zones of increased water saturation and decreased soil respiration.     

Whole-body 3D kinematics of bird take-off: key role of the legs to propel the trunk

Previous studies showed that birds primarily use their hindlimbs to propel themselves into the air in order to take-off. Yet, it remains unclear how the different parts of their musculoskeletal system move to produce the necessary acceleration. To quantify the relative motions of the bones during the terrestrial phase of take-off, we used biplanar fluoroscopy in two species of birds, diamond dove (Geopelia cuneata) and zebra finch (Taeniopygia guttata). We obtained a detailed 3D kinematics analysis of the head, the trunk and the three long bones of the left leg. We found that the entire body assisted the production of the needed forces to take-off, during two distinct but complementary phases. The first one, a relatively slow preparatory phase, started with a movement of the head and an alignment of the different groups of bones with the future take-off direction. It was associated with a pitch down of the trunk and a flexion of the ankle, of the hip and, to a lesser extent, of the knee. This crouching movement could contribute to the loading of the leg muscles and store elastic energy that could be released in the propulsive phase of take-off, during the extension of the leg joints. Combined with the fact that the head, together with the trunk, produced a forward momentum, the entire body assisted the production of the needed forces to take-off. The second phase was faster with mostly horizontal forward and vertical upward translation motions, synchronous to an extension of the entire lower articulated musculoskeletal system. It led to the propulsion of the bird in the air with a fundamental role of the hip and ankle joints to move the trunk upward and forward. Take-off kinematics were similar in both studied species, with a more pronounced crouching movement in diamond dove, which can be related to a large body mass compared to zebra finch.     

Gastral drumming: a nest-based food-recruitment signal in a social wasp

Many social insect species produce signals that either recruit foragers to a specific food source or simply activate more nestmates to become foragers. Both are means of enhancing resource exploitation by increasing the number of individuals devoted to gathering profitable resources. Gastral drumming (GD) has been documented in several species of yellowjackets and hornets (Vespidae: Vespinae). It has been hypothesized that it is a hunger signal, but there is little empirical evidence to support this claim. An alternative hypothesis is that GD recruits workers to forage for food. Here, we report the results of a test between the hunger-signal and food-recruitment hypotheses in the German yellowjacket wasp, Vespula germanica. We show that the rate of performance of GD decreased when colonies were deprived of food and increased when supplemental food was provided. Playback of GD caused increased rates of (1) movement in the nest, (2) trophallaxis, and (3) worker departures from the nest. Together, these results support the conclusion that GD is not a hunger signal as previously asserted but instead is a nest-based food-recruitment signal, the first to be reported for a social wasp.     

Highly modular pattern in ant-plant interactions involving specialized and non-specialized myrmecophytes

Because Tachia guianensis (Gentianaceae) is a “non-specialized myrmecophyte” associated with 37 ant species, we aimed to determine if its presence alters the ant guild associated with sympatric “specialized myrmecophytes” (i.e., plants sheltering a few ant species in hollow structures). The study was conducted in a hilly zone of a neotropical rainforest where two specialized myrmecophytes grow at the bottom of the slopes, another at mid-slope, and a fourth on the hilltops. Tachia guianensis, which occurred everywhere, had its own guild of associated ant species. A network analysis showed that its connections with the four other myrmecophytes were rare and weak, the whole resulting in a highly modular pattern of interactions with one module (i.e., subnetwork) per myrmecophyte. Three ant species parasitized three out of the four specialized myrmecophytes (low nestedness noted), but were not or barely associated with T. guianensis that therefore did not influence the parasitism of specialized myrmecophytes.     

Ecosystem-based adaptation to climate change: defining hotspot municipalities for policy design and implementation in Brazil

We developed an indicator that defines priority municipalities in order to facilitate the deployment of preventive policies and strategies for ecosystem-based adaptation to climate change (EbA) in Brazilian municipalities. Based on the premises that poor people are the population most vulnerable to climate change and that conservation and sustainable use of biodiversity and ecosystems are adaptive to climate change, our indicator uses three parameters: (1) poverty, (2) proportion of natural-vegetation cover, and (3) exposure to climate change. Thus, we searched for Brazilian municipalities that simultaneously belonged to the quartile of municipalities with the highest percentage of poverty, the quartile with the highest percentage of natural-vegetation cover, and the quartile with the highest exposure indices in two global climate models (Eta-HadGEM, Eta-Miroc). We found 398 (7.1%) EbA hotspots among 5565 Brazilian municipalities, which comprise 36% of the total area of native remnants in the country and are home to 22% of the poor people in Brazil. In their majority, these municipalities cover significant portions of the Amazon, Cerrado, Caatinga, and Atlantic forest, and indeed, these regions are recognised as some of the most vulnerable to climate change in the world. Considering the relevance of these biomes for the global water and nutrient cycle (Amazon), global food security (Cerrado), vulnerability to desertification (Caatinga), and biodiversity (all) we discuss the adaptive strategies in place, the need to bring them to scale, and existing policy gaps. Finally, in an effort to guide international and national investment and policies, we discuss how the approach described here can be applied to societies inhabiting tropical forests, savannas, and semiarid zones in other parts of the world. In particular, we propose that the indicator developed here is a simple and fast way to achieve early detection of priority municipalities for deployment of EbA action and policies, particularly in tropical developing countries.     

Chemistry of soil solutions under different kinds of vegetation in the vicinity of a thermal power station

The influence of atmospheric deposition on the chemical characteristics of soil solutions in a small catchment area in NW Spain was studied. The soils, developed from slates, were sampled from seven sites supporting different forms of vegetation (deciduous and pine forest and heath). Soil solutions were extracted, by the column displacement method, from soil samples collected monthly from March 1992 until November 1993. The solutions were acidic with a low content of basic cations. The most common ions in all horizons were Cl(-) and Na(+), due to marine influence. In the surface horizons (0-10 cm), relatively high concentrations of SO(2-)4 (150-380 micromol litre(-1)) and Zn (approximately 2 micromol litre(-1)) were obtained, with good correlation between the two ions. These results, along with the prevalence of inorganic forms of Al (50-90% of total Al), were related to the effects of acidic deposition in the catchment area. The more rapid breakdown of litter in the soils under deciduous forest explains the greater ionic concentrations obtained in these solutions.     

Palygorskite as a feasible amendment to stabilize heavy metal polluted soils

The sorption behaviour of palygorskite has been studied with respect to lead, copper, zinc and cadmium in order to consider its application to remediate soils polluted with these metals. The Langmuir model was found to describe well the sorption processes offering maximum sorption values of 37.2 mg/g for lead, 17.4 mg/g for copper, 7.11 mg/g for zinc and 5.83 mg/g for cadmium at pH 5-6. In addition the effect of palygorskite amendment in a highly polluted mining soil has been studied by means batch extractions and leaching column studies. The soluble metal concentrations as well as the readily-extractable metal concentrations were substantially decreased at any concentration of palygorskite applied to soil (1, 2, 4%), although the highest decrease is obtained at the 4% dose. The column studies also showed a high reduction in the metal leaching (50% for lead, 59% for copper, 52% for zinc and 66% for cadmium) when a palygorskite dose of 4% was applied.     

Changes in yolk total proteins and lipid components and embryonic growth rates during lobster (<Emphasis Type="Italic">Homarus americanus</Emphasis>) egg development under a simulated seasonal temperature cycle

From August 2000 to June 2001, seven egg-carrying female lobster (Homarus americanus) from the Îles de la Madeleine population (Gulf of St. Lawrence, Canada) were held under a simulated seasonal temperature cycle to monitor egg development from extrusion to hatching. For the first time, changes in the yolk components (total lipids and major lipid classes, total proteins) and embryo growth of single eggs were monitored separately over the entire development period. Under the controlled temperature conditions, egg development proceeded in three phases. (1) Autumn, from extrusion to early December, was marked by a rapid increase in the Perkinss eye index and rapid declines in yolk total proteins and triacylglycerols (TAG). Embryo daily growth rate was estimated between 1 and 2 µg proteins day^–1. (2) Winter, from late December to early April (temperature stable at ca. 1°C) was characterized by a stationary phase in the evolution of the eye index and yolk lipid use, and embryo growth slowed significantly. (3) Spring, from late April to hatching in June was the period with the most rapid changes in yolk TAG and embryo growth rates >6 µg proteins day^–1 were recorded. Almost 65% of the live biomass (total proteins) of the hatching larvae was accumulated during the last few weeks of development. An index of embryo growth efficiency was estimated as the slope of the relationship between embryo total proteins and yolk TAG during egg development. A relationship was found between the initial mean egg dry weight and the embryo growth efficiency index suggesting that under the same experimental conditions bigger eggs used yolk lipids more efficiently and sustained faster embryonic growth than smaller eggs. The relationship may also explain why larger larvae originate from larger eggs.Communicated by R.J.Thompson, St Johns     

Chemical defense of the ladybird beetle Epilachna paenulata

Summary. The defensive chemistry of the ladybird beetle Epilachna paenulata (Coleoptera: Coccinellidae) was characterized as a mixture of piperidine, homotropane and pyrrolidine alkaloids. Whole body extracts of adult beetles contain four major alkaloids: 1-(6-Methyl-2,3,4,5-tetrahydro-pyridin-2-yl)-propan-2-one; 1-(6-methyl-2-piperidyl)-propan-2-one; 9-aza-1-methyl-bicyclo[3.3.1]nonan-3-one and 1- (2′′- hydroxyethyl)-2-(12′-aminotridecyl)-pyrrolidine. Comparative studies of the defensive chemistry of eggs, larvae, pupae and adults showed both qualitative and quantitative differences in alkaloid composition among the four life stages, and also within adult age. Laboratory predation bioassays with wolf spiders showed that the adults are better protected than the larvae and pupae. Field tests showed the adult alkaloid extract to be deterrent to ants.