Hydrolytic degradation of azimsulfuron, a sulfonylurea herbicide

The chemical degradation of the herbicide azimsulfuron was investigated in aqueous solutions at different pH values. The hydrolysis rate, determined by HPLC analyses, was pH dependent and was much faster in acidic than in neutral or weakly basic conditions. The metabolites formed at different pH values were compared with standards when possible or isolated and identified using ESI-LC-MS/MS, (1)H NMR and (13)C NMR. The two main products of hydrolysis in mild acidic solution were identified as 2-amino-4,6-dimethoxy-pyrimidine and 2-methyl-4-(2-methyl-2H-tetrazol-5-yl)-2H-pyrazole-3-sulfonamide, both produced as a result of the sulfonylurea bridge cleavage. Under basic conditions, a new product, a substituted 2-pyrimidinamine, deriving from the contraction of the sulfonylurea bridge, was isolated and completely characterized for the first time.     

Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid

A lignite humic acid (HA) was fractionated by preparative high performance size-exclusion chromatography (HPSEC) in seven different size-fractions. The size-fractions were characterized by cross polarization (CP) magic angle spinning (MAS) (13)C NMR spectroscopy and a further analytical HPSEC elution under UV and fluorescence detection. The alkyl hydrophobic components mainly distributed in the largest molecular-size-fraction, whereas the amount of oxidized carbons increased with decreasing size of fractions. Cross polarization time (T(CH)) and proton spin-lattice relaxation time in the rotating frame (T(1rho)(H)) were measured from variable contact time (VCT) experiments. The bulk HA was characterized by the shortest T(CH) values and the longest T(1rho)(H) values which suggested, respectively, one. an aggregation of components in a large conformation that favored a fast H-C cross polarization, and, two. consequent steric hindrances that prevented fast local molecular motions and decreased proton relaxation rates. Conversely, the separated size-fractions showed longer T(CH) values and shorter T(1rho)(H) values than the bulk HA, thereby indicating that they were constituted by a larger number of mobile molecular conformations. The UV and fluorescence absorptions were both low in the large size-fractions that mainly contained alkyl carbons, whereas they increased in the olephinic- and aromatic-rich fractions with intermediate molecular-size, and decreased again in the smaller fractions which were predominantly composed by oxidized carbons. These results support the supramolecular structure of humic substances and indicate that the observed variation in conformational distribution in humic association may be used to explain environmental processes with additional precision.     

Possible effects of persistent organochlorinated pollutants cocktail on thyroid hormone levels and pituitary-thyroid interrelations

In polluted district of Michalovce in East Slovakia (POLL) and two districts with background pollution (BCGR) 2046 adults (834 males and 1212 females aged 20-75 years) were examined. Serum levels of thyrotropin (TSH), free thyroxine (FT4), total triiodothyronine (TT3) and antithyroperoxidase antibodies (TPOab) were estimated by electrochemiluminiscent assay and also these of 15 polychlorinated biphenyl congeners (PCBs), p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane were measured by high resolution gas chromatography/mass spectrometry. In addition, also dioxins, furans, coplanar- and mono-ortho-PCBs as well as selected hydroxylated and methylsulphonated PCBs and DDE metabolites were measured by appropriate methods based on gas chromatography/mass spectrometry principle. In POLL significantly higher levels of all organochlorines were found than these in BCGR. When pooled values from both areas were stratified in terms of PCBs level and treated as continuous variables, positive association of PCBs with FT4 and TT3 was found, the latter two being also mutually associated. However, within the category of PCBs level <530 ng/glipid (n=232) the association between PCBs and both the FT4 (p<0.09) and TT3 (p<0.03) was negative and any association of these was not found within the category of PCBs level of 531-1000 ng/g (n=691). In contrast, in the category of 531-2000 ng/g (n=1307) positive association appeared between PCBs and FT4 (p<0.001) as well as TT3 (p<0.05). Highly significant association of PCBs with FT4 (p<0.001) was further found in the categories with PCBs level of 1001-101414 ng/g (n=1307) and 2001-101414 (n=1123), while significant association with TT3 was observed only in the category of 531-2000 ng/g. Such findings suggest possible threshold level in positive effect of PCBs on FT4 and TT3 level which seems to be individual and located somewhere around the PCBs level of 1000 ng/g. However, highly significant negative association of both FT4 and TT3 with TSH was found in each of above indicated PCBs categories. Considerable difference in FT4 and TT3 level between large groups of subjects with the same range of PCBs level was also found suggesting different individual susceptibility to the effects of organochlorines. Among a total of 26 cases from POLL with very low TSH level (<0.5 mU l(-1)) 13 cases showed very high level of PCBs, FT4 and TT3, thus supporting a hypothesis on a novel sporadic form of high PCBs related peripheral subclinical hyperthyroidism possibly resulting from the long-term disruption of equilibrium between bound and free thyroxine in plasma by high PCBs level followed by a striking inhibition of TSH release from the pituitary.     

Lisbon’s womb: an approach to the city metabolism in the turn to the twentieth century

The consumption and production of food products in the municipality of Lisbon in the 1890–1900 decade is assessed with the support of historical cartography and statistical resources. For the first time, food production in a municipality in the turn to the twentieth century is accounted and simultaneously subject of a visual analysis of the land used for agriculture and of the water infrastructures that supported such uses. Agriculture occupied at least 40 % of the territory of the city, while the built environment occupied no more than 16 % of the territory. However, local production of food was far from supplying most of the citizens’ needs, and substantial food imports were needed. In this context, the municipality behaved like a heterotrophic system, highly dependent on the external supply of resources. Moreover, comparing to other European cities at the time Lisbon was facing in the end of the nineteenth century a late and slow transition from an agrarian social metabolism to an industrial one, suggesting that Lisbon was still relatively high-solar-powered as compared to other European cities at the time that were already highly fossil-fuel-powered.     

Production, consumption, and general equilibrium with physical constraints

This paper analyzes the consequences of integrating the conservation laws of mass and energy into the microeconomic models of production, consumption, and general equilibrium. We show that abstract models and especially general equilibrium theory are consistent with these physical constraints, but most applied and environmental economic models are not. We analyze the consequences of physical conservation laws for substitution possibilities and show that these constraints limit the number of independent substitution processes but not the value of the substitution elasticities. Finally, we propose a method for integrating physical constraints into static microeconomic models with a minimum of changes.     

Chemical recycling of poly(ethylene terephthalate) (pet) by hydrolysis and glycolysis

In this paper we review an interesting method of PET recycling, i.e. chemical recycling; it is based on the concept of depolymerizing the condensation polymer through solvolytic chain cleavage into low molecular products which can be purified and reused as raw materials for the production of high-quality chemical products. In this work our attention is confined to the hydrolysis (neutral, acid and alkaline) and glycolysis processes of PET chemical recycling; operating conditions and mechanism of each method are reported and described. The neutral hydrolysis has an auto accelerating character; two kinetic models have been proposed: an half-order and a second order kinetic model. The acid hydrolysis could be explained by a modified shrinking core model under chemical reaction control and the alkaline hydrolysis by a first-order model with respect to hydroxide ion concentration. To describe glycolysis, two different kinetic models have been proposed where EG can act or not as internal catalyst. Further experimental and theoretical investigations are required to shed light on the promising processes of PET chemical recycling reviewed in this work.     

Effect of parentage and relatedness on the individual contribution to cooperative chick care in carrion crows Corvus corone corone

Carrion crows Corvus corone corone in northern Spain form complex cooperative groups that contain non-dispersing offspring and immigrants. Reproduction is often shared among group members, with polyandry prevalent over joint egg laying. However, due to incest avoidance or sexual immaturity, reproduction is potentially available only to a fraction of group members (potential breeders), while others do not breed (non-breeders). We combined molecular data with video-recorded observations at nests in order to investigate whether potential breeders and non-breeders adjust their individual effort in nestling feeding respectively to their level of parentage and the relatedness with the chicks. Overall, parents of at least one chick in the brood showed the highest feeding rates. Among potential breeders, genetic mothers and fathers fed chicks at significantly higher rates than individuals with no parentage, but they did not adjust their effort according to the proportion of offspring generated. Current direct fitness benefits are therefore important in determining a high provisioning effort, but crows may lack a mechanism to finely assess their share of parentage. Among non-breeders, males contributed more than females to chick feeding, but we found no significant correlation between feeding rate and relatedness to the nestling. We discuss how the latter result can be reconciled with the fact that kin selection has been shown to be important in shaping the crow cooperative society.Communicated by C. Brown     

Chaos and pattern formation in a spatial tritrophic food chain

The model of Hastings and Powell describes a tritrophic food chain that exhibits chaotic dynamics. The model assumes that the populations are homogeneously mixed, so that the probability that any two individuals interact is uniform and space can be ignored. In this paper we propose a spatial version of the Hastings and Powell model in which predators seek their preys only in a finite neighborhood of their home location, breaking the mixing hypothesis. Treating both space and time as discrete variables we derive a set of coupled equations that describe the evolution of the populations at each site of the spatial domain. We show that the introduction of local predator–prey interactions result in qualitatively distinct dynamics of predator and prey populations. The evolution equations for the predators involve averages over the local density of preys, whereas the equations for the preys involve double averages, where the local density of both preys and predators appear. Our numerical simulations show that local predation also leads to spontaneous pattern formation and to qualitative changes in the global dynamics of the system. In particular, depending on the size of the predation neighborhoods, the chaotic strange attractor present in the original model of Hastings and Powell can be replaced by a stable fixed point or by an attractor of simpler topology.     

False feedings at the nests of carrion crows<Emphasis Type="Italic"> Corvus corone corone</Emphasis>

False feedings, when individuals visit the nest but refrain from feeding the chicks, occur in some cooperative species and have been interpreted in the white-winged chough (Corcorax melanorhamphos) as active deception by helpers towards the rest of the group. In a cooperatively breeding population of carrion crows (Corvus corone corone) 81.5% of the individuals that provided nestling care showed various kinds of false feedings: arriving at the nest with no food, consuming part or all the food brought to the nest, or taking back from a chicks gape the food that had just been delivered. False feedings occurred on average during 16.3% of nest visits, with some individuals performing them at very high rates (up to 64% of nest visits). False feedings occurred at similar rates in unassisted pairs and groups with helpers, and breeding females showed false feeding at significantly higher rates than other group members. Furthermore, individuals showed false feedings regardless of whether they were alone on the nest or in the presence of other group members, and false feedings did not provoke aggression by the rest of the group. False feedings are not likely to represent deceptive help in the carrion crow. We suggest that crows evaluate the chicks condition during nest visits and that false feedings occur as result of a trade-off between their own hunger and the chicks needs.Communicated by W.A. Searcy