Dye-sensitized photodegradation of the fungicide carbendazim and related benzimidazoles

The present work studies the visible-light-promoted photodegradation of the colorless fungicide carbendazim (methyl 2-benzimidazolecarbamate) and several 2-substituted benzimidazoles (SBZ's), in water or water-methanol solution, in the presence of air and, as a photosensitizer, the synthetic xanthene dye Rose Bengal (RB) or the natural pigment riboflavin (Rf). The results indicate that the degradation of each particular SBZ depends on its chemical structure and on the sensitizer employed. In the presence of RB, the degradation always operates via a singlet molecular oxygen (O(2)((1)Delta(g)))-mediated mechanism, through a highly efficient process, as deduced from the comparison of the rate constants for physical and chemical quenching of O(2)((1)Delta(g)). In the presence of Rf, the visible-light irradiation of any of the studied SBZ's produces a series of competitive processes that depend on the relative concentrations of Rf and SBZ. These processes include the quenching of excited singlet and triplet Rf states by the SBZ and the generation of both O(2)((1)Delta(g)) and superoxide radical anion (O(2)(-)), the latter generated by electron transfer from excited Rf species to the dissolved oxygen. The overall result is the photodegradation of the SBZ and the photoprotection of the sensitizer.     

Studies of the behaviour and fate of the polymer-additives octadecyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate and tri-(2.4-di-t-butylphenyl)phosphite in the environment.

In order to evaluate the environmental risk potential of the polymer-additives octadecyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate (additive 1) and tri-(2.4-di-t-butylphenyl)phosphite (additive 2) we have studied the degradation of the 14C-labelled single components and their release from a polypropylene matrix in abiotic and biotic test systems as well as their transport behaviour in soil. The biotic degradation in waste compost, activated sludge and in soil was studied. In order to conduct release tests, waste disposal material were used as well. The abiotic degradation was effectuated by photooxidation at a catalytic surface. The highest mineralisation rates were obtained by photooxidative degradation of the two test substances. The maximum content of bounded residues was found for additive 1 in soil and for additive 2 in waste compost. In the extracts of soil and compost, the principal metabolites could be identified in the case of additive 1 as 7.9-di-t-butyl-1-oxaspiro[4.5]deca-6.9-dien-2.8-dion and in activated sludge as the methyl ester of 3-(3.5-di-t-butyl-4-hydroxyphenyl) propionic acid. Additive 2 metabolised in all degradation tests nearly completely under formation of two products. The main component was identified as tri-(2.4-di-t-butylphenyl)phosphate. Both polymer-additives were eluated from the chosen soil types. The transport behaviour of additive 1 was independent from the soil type. In all test matrices additive 1 as well as additive 2 were released from polypropylene. Because the amounts of additive 1 and 2 absorbed onto soil particles were taken into account, the highest liberation rates were found in the soil test.     

Effect of chlorophenolic pesticides on the photochemistry of riboflavin

The possibility of riboflavin sensitized photo‐oxidation of polychlorinated pesticides was investigated. The dye proved to be an inefficient sensitizer for that purpose, when irradiated with visible light, in aereated aqueous solutions. A quenching of singlet and triplet excited states of the chromophore (depending on the concentrations of the quencher) is responsible for this failure in the photo‐degradation of the pesticides, which resulted easily oxidizable, via singlet oxygen mechanism, when proflavine was employed as a sensitizer. Parallel, and as a direct consequence, the rate of aerobic riboflavin photobleaching decreased drastically in the presence of the chlorophenols.

The implication of our results on the inhibition of riboflavin degradation by the presence of chlorinated phenolic pesticides in the environment, is discussed, from the point of view of a kinetic and mechanistic study.     

Cumulative ecological and socioeconomic effects of forest policies in coastal Oregon.

Forest biodiversity policies in multi-ownership landscapes are typically developed in an uncoordinated fashion with little consideration of their interactions or possible unintended cumulative effects. We conducted an assessment of some of the ecological and socioeconomic effects of recently enacted forest management policies in the 2.3-million-ha Coast Range Physiographic Province of Oregon. This mountainous area of conifer and hardwood forests includes a mosaic of landowners with a wide range of goals, from wilderness protection to high-yield timber production. We projected forest changes over 100 years in response to logging and development using models that integrate land use change and forest stand and landscape processes. We then assessed responses to those management activities using GIS models of stand structure and composition, landscape structure, habitat models for focal terrestrial and aquatic species, timber production, employment, and willingness to pay for biodiversity protection. Many of the potential outcomes of recently enacted policies are consistent with intended goals. For example, we project the area of structurally diverse older conifer forest and habitat for late successional wildlife species to strongly increase. 'Other outcomes might not be consistent with current policies: for example, hardwoods and vegetation diversity strongly decline within and across owners. Some elements of biodiversity, including streams with high potential habitat for coho salmon (Oncorhynchus kisutch) and sites of potential oak woodland, occur predominately outside federal lands and thus were not affected by the strongest biodiversity policies. Except for federal lands, biodiversity policies were not generally characterized in sufficient detail to provide clear benchmarks against which to measure the progress or success. We conclude that land management institutions and policies are not well configured to deal effectively with ecological issues that span broad spatial and temporal scales and that alternative policies could be constructed that more effectively provide for a mix of forest values from this region.     

Robust, comparable population metrics through collaborative photo-monitoring of whale sharks Rhincodon typus.

The formulation of conservation policy for species that are rare and migratory requires broad cooperation to ensure that adequate levels of standardized data collection are achieved and that the results of local analyses are comparable. Estimates of apparent survival rate, relative change in abundance, and proportions of newly marked and returning individuals can inform local management decisions while highlighting corresponding changes at other linked research stations. We have applied computer-assisted photo-identification and mark-recapture population modeling to whale sharks Rhincodon typus at Ningaloo Marine Park (NMP), Western Australia, to create a baseline trend for comparison with other regional aggregations of the species. We estimate several ecological parameters of interest, including an average apparent survival rate of 0.55 yr(-1) for sharks newly marked (new) and 0.83 yr(-1) for sharks captured in multiple seasons (philopatric). The average proportion of philopatric sharks is found to be 0.65 of the total population, and we derive an average population growth rate of 1.12 yr(-1) for them. Our analysis uncovered significant heterogeneity in capture and survival probabilities in this study population; our chosen model structures and data analysis account for these influences and demonstrate a good overall fit to the time-series data. The results show good correspondence between capture probability and an available measure of recapture effort, suggesting that unmodeled systematic effects contribute insignificantly to the model fits. We find no evidence of a decline in the whale shark population at NMP, and our results provide metrics of value to their future management. Overall, our study suggests an effective approach to analyzing and modeling mark-recapture data for a rare species using computer-assisted photo-identification and opportunistic data collection from ecotourism to ensure the quality and volume of data required for population analysis.