Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Growth,mortality and recruitment of the yellow clam Mesodesma mactroides on Uruguayan beaches

We studied some aspects of the population dynamics of the yellow clam Mesodesma mactroides (Deshayes, 1854) which inhabits the eastern sandy beaches of Uruguay. Observations were made from March 1983 through March 1985 (harvesting season), and additional data from January 1988 to December 1989 (closed season) were also included in the analyses. Parameters of growth and mortality were estimated by methods that make use of age or length information. An age/length relationship was constructed by counting growth rings. Results were consistent with those obtained with modal class progression analysis and other length/frequency methods. The growth curve obtained from the age/length relationship did not account for seasonality in growth rate, and a seasonal growth model explained growth oscillations in a better way. The instantaneous coefficient of natural mortality (M) estimated for the closed season was 1.64, whereas an increase in fishing mortality (F) was observed during 1984. Age composition did not change during the 2 yr of study, and the first 6 mm class accounted for over 50% of the population. The main contribution of recruits was observed between late summer and early fall (February to April), and the recruitment pattern suggested one main settlement period per year. Growth and recruitment success appeared to be regulated by density-dependence processes. Some implications for management are considered in this context. Methodological aspects concerning the reliability of empirical equations and programs for estimating growth and mortality are discussed.     

Acoustic analysis of blast waves produced by rapid phase transition of LNG released on water

Massive offshore and onshore storage of fuel have led the international community to raise questions about the hazards on the surrounding installations and people. Among the possible accidental scenarios when cryogenic gas as liquefied natural gas (LNG) is spilled on water at a very fast rate, the phenomenon of rapid phase transition (RPT) may occur: large amounts of energy are released during phase transition which can generate explosions. The related consequences should be added to the possible consequences of fire in terms of flash fire, fireball, pool fire, and vapour cloud explosion for confined and congested geometry surrounding the release point.In this paper, the analysis of RPT of LNG has been studied from the point of view of blast wave production, through ab initio acoustic analysis for monopole source. Maximum overpressures, as calculated at the source point and along the blast pathway are compared with results of large scale experiments. Safety distances are given for the sake of comparison with threshold distances reported in the open literature.     

State space models with spatial deformation

Space deformation has been proposed to model space-time varying observation processes with non-stationary spatial covariance structure under the hypothesis of temporal stationarity. In real applications, however, the temporal stationarity assumption is inappropriate and unrealistic. In this work we propose a spatial-temporal model whose temporal trend is modeled through state space models and a spatially varying anisotropy is modeled through spatial deformation, under the Bayesian approach. A distinctive feature of our approach is the consideration of model uncertainty in an unified framework. Our model has a clear advantage over the ones proposed so far in the literature when the main objective of the study is to perform spatial interpolation for fixed points in time. Approximations of the posterior distributions of the model parameters are obtained via Markov chain Monte Carlo methods. This allows for prediction of the process values in space and time as well as handling of missing values. Two applications are presented: the first one to model concentrations of sulfur dioxide in the eastern United States and the second one to model monthly minimum temperatures in the State of Rio de Janeiro.     

Using network centrality measures to manage landscape connectivity

We use a graph-theoretical landscape modeling approach to investigate how to identify central patches in the landscape as well as how these central patches influence (1) organism movement within the local neighborhood and (2) the dispersal of organisms beyond the local neighborhood. Organism movements were theoretically estimated based on the spatial configuration of the habitat patches in the studied landscape. We find that centrality depends on the way the graph-theoretical model of habitat patches is constructed, although even the simplest network representation, not taking strength and directionality of potential organisms flows into account, still provides a coarse-grained assessment of the most important patches according to their contribution to landscape connectivity. Moreover, we identify (at least) two general classes of centrality. One accounts for the local flow of organisms in the neighborhood of a patch, and the other accounts for the ability to maintain connectivity beyond the scale of the local neighborhood. Finally, we study how habitat patches with high scores on different network centrality measures are distributed in a fragmented agricultural landscape in Madagascar. Results show that patches with high degree and betweenness centrality are widely spread, while patches with high subgraph and closeness centrality are clumped together in dense clusters. This finding may enable multispecies analyses of single-species network models.     

Comparative aspects of sexual reproduction in the Caribbean coral genus Diploria (Scleractinia: Faviidae)

The increasing decline of Caribbean reef-building species underlines the importance of more information on their reproductive biology and ecology. This study compares the reproductive biology of the three species of Diploria, an important Caribbean reef-building genus affected by bleaching and disease, by: (a) characterizing their gametogenetic cycles simultaneously, (b) exploring the spatial and temporal variability in reproductive traits within and across species, (c) assessing fecundity and the minimum size of sexual reproduction, and (d) comparing information with other studies in the Caribbean. Starting in 1999, one tissue core was collected every month (for 17 months) from each of at least five large, tagged colonies of each species in La Parguera, Puerto Rico. Three more temporally spaced samplings were done during summer of 2000 and winter–spring of 2001 and 2002. Tissues were fixed in Helly’s solution, rinsed in fresh water, decalcified with 10% HCl, and preserved in 70% ethanol, embedded in paraplast, cut, and thin slides (7 μm) prepared and stained with Heidenhain’s Aniline-Blue method. Maximum egg size, number of eggs and spermaries were measured and gametogenetic cycles assessed. Microscopic observations confirmed that all three species were simultaneous hermaphrodites with a single, annual gametogenetic cycle. Spermatocytes and oocytes developed within the same mesentery but were not intermingled. Female gametes developed several months earlier than that of males, but both reached maturation simultaneously. Minor differences in the onset of gametogenesis were found for D. strigosa and D. clivosa, with both spawning after 10 p.m. between 8 and 10 days after the August and/or September full moons. D. labyrinthiformis on the other hand, began oogenesis in early July and spawned after 11 p.m. between 7 and 10 days after the April and/or May full moons. Spatial and temporal variability in mean number of spermaries and eggs/mesentery among colonies within and among species were found. D. labyrinthiformis had consistently significant higher mesenterial and polyp fecundity compared to the other two species over the 3 years. Average egg diameter varied between 240 and 246 μm and was similar among the three species. D. strigosa and D. clivosa sexual reproductive characteristics were similar to those of other large broadcast spawning Faviidae (i.e. Montastraea spp) in the region. In contrast, D. labyrinthiformis was a spring spawner (similar to Colpophyllia natans in Puerto Rico), which together with its significantly different micromorphology suggests that it might be phylogenetically more distant to the other taxa.     

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.