Treatment of phenylmercury salts by heterogeneous photocatalysis over TiO(2)

UV/TiO(2) photocatalysis of phenylmercury salts in aqueous solutions has been performed starting from both acetate (C(6)H(5)HgCH(3)CO(2), PMA) and chloride (C(6)H(5)HgCl, PMC) salts, in the presence or the absence of oxygen at acidic pH. Removal of Hg(II) in solution took place with the simultaneous deposit of dark or pale gray solids on the photocatalyst, identified as metallic Hg (when starting from PMA) or mixtures of Hg(0) and Hg(2)Cl(2) (when starting from PMC). Partial mineralization of the organic part of both compounds has also been achieved. Hg(II) removal and mineralization were enhanced in the absence of oxygen. PMA photocatalysis followed a saturation kinetics, going from first order at low concentration to zero order at higher concentrations (>0.5mM). For PMA, reaction was faster at high pH (11) with formation of mixtures of Hg and HgO. Phenol was detected as a product of the reaction in both cases, PMA and PMC, and no formation of dangerous methyl- or ethylmercury species was observed in the first case. A mechanism for the photocatalytic reaction has been proposed. The fact that calomel was found as a deposit when starting from PMC under nitrogen suggests that the mechanism of Hg(II) transformation proceeds through successive one-electron transfer reactions passing by mercurous forms.     

Total mercury, organic mercury and selenium in liver and kidney of a South American coastal dolphin

Selenium and total and organic mercury were determined in the liver and kidney of franciscana dolphin (Pontoporia blainvillei) incidentally caught in fishing nets along two Brazilian coastal areas (southeast and south). Regional differences in the concentrations of these contaminants were observed in P. blainvillei. Liver showed the highest organic and total mercury. In general, samples of individuals collected at the southern of Brazil had the highest concentrations of selenium and total and organic mercury. No significant gender differences were observed. Growth stage influenced the accumulation of these contaminants in both organs, and hepatic concentrations increased with the body length, according to the sampling area. Molar mercury and selenium concentrations in liver were significantly correlated, with a Se:Hg ratio close to 4. The among-site differences we found may be related to differences in preferred prey, bioavailability in the marine environment, environmental conditions, or these individuals may belong to distinct populations.     

Adaptation of the chlorophycean Dictyosphaerium chlorelloides to stressful acidic, mine metal-rich waters as result of pre-selective mutations

Several species of microalgae, closely related to mesophilic lineages, inhabit the extreme environment (pH 2.5, high levels of metals) of the Spain's Aguas Agrias Stream water (AASW). Consequently, AASW constitutes an interesting natural laboratory for analysis of adaptation by microalgae to extremely stressful conditions. To distinguish between the pre-selective or post-selective origin of adaptation processes allowing the existence of microalgae in AASW, a Luria-Delbrück fluctuation analysis was performed with the chlorophycean Dictyosphaerium chlorelloides isolated from non-acidic waters. In the analysis, AASW was used as selective factor. Preselective, resistant D. chlorelloides cells appeared with a frequency of 1.1 x 10(-6) per cell per generation. AASW-resistant mutants, with a diminished Malthusian fitness, are maintained in non-extreme waters as the result of a balance between new AASW-resistant cells arising by mutation and AASW-resistant mutants eliminated by natural selection (equilibrium at c. 12 AASW-resistants per 10(7) wild-type cells). We propose that the microalgae inhabiting this stressful environment could be the descendents of chance mutants that arrived in the past or are even arriving at the present.     

Effects of howler monkey reintroduction on ecological interactions and processes

Rewilding has been an increasingly popular tool to restore plant–animal interactions and ecological processes impaired by defaunation. However, the reestablishment of such processes has seldom been assessed. We investigated the restoration of ecological interactions following the reintroduction of the brown howler monkey (Alouatta guariba) to a defaunated Atlantic forest site. We expected the reintroduction to restore plant–animal interactions and interactions between howlers and dung beetles, which promote secondary seed dispersal. We estimated the number of interactions expected to be restored by the reintroduction to provide the baseline interaction richness that could be restored. We followed the reintroduced howler monkeys twice a week for 24 months (337 hours total) to assess their diet. We used howler monkey dung in secondary seed dispersal experiments with 2484 seed mimics to estimate the removal rates by dung beetles and collected the beetles to assess community attributes. We compared the potential future contribution of howler monkeys and other frugivores to seed dispersal based on the seed sizes they disperse in other areas where they occur. In 2 years, howler monkeys consumed 60 animal-dispersed plant species out of the 330 estimated. Twenty-one dung beetle species were attracted to experimentally provided dung; most of them were tunnelers, nocturnal, and large-sized (>10 mm). On average 30% (range 0–100%) of the large seed mimics (14 mm) were moved by dung beetles. About 91% of the species consumed by howlers (size range 0.3–34.3 mm) overlapped in seed size with those removed by dung beetles. In our study area, howler monkeys may consume more large-seeded fruit species than most other frugivores, highlighting their potential to affect forest regeneration. Our results show reintroductions may effectively restore ecological links and enhance ecological processes.     

Characterisation of black carbon-rich samples by <Superscript>13</Superscript>C solid-state nuclear magnetic resonance

There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de índio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. ¹³C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, ¹H-¹³C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the π pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp—variable amplitude CP (VACP)—VACP/MAS pulse sequence, and composite π pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.     

Volatile carbonylic compounds in downtown Santiago, Chile

Formaldehyde, acetaldehyde, acetone, propanal, butanal, 2-butenal, 3-methylbutanal, hexanal, benzaldehyde, 2-methylbenzaldehyde, and 2,5-dimethylbenzaldehyde were measured during six spring days at downtown Santiago de Chile. Measurements were performed 24h/day and averaged over three hour periods. The averages of the maxima (ppbv) were, formaldehyde: 3.9+/-1.4; butanal: 3.3+/-3.4; acetaldehyde: 3.0+/-0.9; acetone: 2.4+/-1.0; 2-butenal: 0.56+/-0.52; propanal: 0.46+/-0.21; benzaldehyde: 0.34+/-0.3; 3-butanal: 0.11+/-0.05; hexanal: 0.11+/-0.08; 2-methylbenzaldehyde: 0.08+/-0.05; 2,5-dimethylbenzaldehyde: 0.05+/-0.03. Aliphatic aldehydes (C1-C3) are strongly correlated among them and weakly with primary (toluene) and secondary (ozone plus nitrogen dioxide or PAN) pollutants. In particular, the correlation between acetaldehyde and propanal values remains even if diurnal and nocturnal data are considered separately, indicating similar sources. All these aldehydes present maxima values in the morning (9-12h) and minima at night (0-3h). The best correlation is observed when butanal and 2-butenal data are considered (r=0.99, butanal/2-butenal=6.2). These compounds present maxima values during the 3-6h period, with minima values in the 0-3h period. These data imply a strong pre-dawn emission. Other aldehydes show different daily profiles, suggesting unrelated origins. Formaldehyde is the aldehyde whose concentration values best correlate with the levels of oxidants. The contribution of primary emissions and photochemical processes to formaldehyde concentrations were estimated by using a multiple regression. This treatment indicates that (32+/-16)% of measured values arise from direct emissions, while (79+/-23)% is attributable to secondary formation.     

Agroecosystem energy transitions in the old and new worlds: trajectories and determinants at the regional scale

Energy efficiency in biomass production is a major challenge for a future transition to sustainable food and energy provision. This study uses methodologically consistent data on agroecosystem energy flows and different metrics of energetic efficiency from seven regional case studies in North America (USA and Canada) and Europe (Spain and Austria) to investigate energy transitions in Western agroecosystems from the late nineteenth to the late twentieth centuries. We quantify indicators such as external final energy return on investment (EFEROI, i.e., final produce per unit of external energy input), internal final EROI (IFEROI, final produce per unit of biomass reused locally), and final EROI (FEROI, final produce per unit of total inputs consumed). The transition is characterized by increasing final produce accompanied by increasing external energy inputs and stable local biomass reused. External inputs did not replace internal biomass reinvestments, but added to them. The results were declining EFEROI, stable or increasing IFEROI, and diverging trends in FEROI. The factors shaping agroecosystem energy profiles changed in the course of the transition: Under advanced organic and frontier agriculture of the late nineteenth and early twentieth centuries, population density and biogeographic conditions explained both agroecosystem productivity and energy inputs. In industrialized agroecosystems, biogeographic conditions and specific socio-economic factors influenced trends towards increased agroecosystem specialization. The share of livestock products in a region’s final produce was the most important factor determining energy returns on investment.

     

Isolation and characterization of a Pseudomonas aeruginosa from a virgin Brazilian Amazon region with potential to degrade atrazine

The use of pesticides to increase agricultural production can result in the contamination of the environment, causing changes in the genetic structure of organisms and in the loss of biodiversity. This practice is also inducing changes in the rainforest ecosystem. In this work, a Pseudomonas aeruginosa isolated from a preservation soil area of the Brazilian Amazon Forest, without usage of any pesticide, was evaluated for its potential to degrade atrazine. This isolate presented all responsible genes (atzA, atzB, atzC, atzD, atzE, and atzF) for atrazine mineralization and demonstrated capacity to use atrazine as a nitrogen source, having achieved a reduction of 44 % of the initial concentration of atrazine after 24 h. These results confirm gene dispersion and/or a possible contamination of the area with the herbicide, which reinforces global concern of the increase and intensive use of pesticides worldwide.