Photocatalytic degradation of trinitrotoluene and other nitroaromatic compounds

The photocatalytic degradation of 2,4,6-trinitrotoluene and ten other nitroaromatic compounds in aerated TiO₂ suspensions has been studied. The following order of reactivity was observed: nitrotoluenes > nitrobenzene > dinitrotoluenes . dinitrobenzenes > 2,4,6-trinitrotoluene > 1,3,5-trinitrobenzene, which reflects the known influence of nitro groups towards the attack of electrophilic reagents on the aromatic molecule.     

Reconstructed mass-spectrometric pattern for characterization of carbon compounds in smoker's lung in situ

BACKGROUND: Cigarette smoke is a major anthropogenic pollutant and contributes to the permanent load of ambient particulate matter in the air, particularly indoors. It is the leading risk factor for premature loss of life due to chronic bronchitis, emphysema and lung cancer. Smoker's lung and graphite pneumoconiosis are pathological states characterized by the deposition of carbonaceous particles. METHODS: Mass spectrometry was used to evaluate unstained lung sections obtained in vivo from a heavy smoker and a patient with occupationally acquired graphite pneumoconiosis. RESULTS AND DISCUSSION: The composition of carbon compounds deposited in lung tissue samples is demonstrated here for the first time. Thirty carbonaceous-containing microareas from ten biopsies (three areas per biopsy) of lung tissues were analyzed mass-spectrometrically. In each case, the samples were taken from a smoker's lung or those demonstrating a graphite pneumoconiosis. The lung-tissue samples were selected by light microscopy before they were evaporated for mass spectrometry. First-order criteria were anionic and cationic mass peaks which occur within the mass patterns in lung tissues of smoker's lung, although not in graphite pneumoconiosis. Second-order criteria were mass peaks from smoker's lung with standard deviations SD < or = 14% of the mean value. First and second-order mass peaks matched the mass peaks of experimental cigarette-smoke condensate in 9 out of 11 peaks. A software program was developed that enabled fast, automated recognition of the typical mass peaks, and thereby confirmed the histological diagnosis of smoker's lung. CONCLUSIONS: The analysis of carbonaceous particles within lung biopsies from a heavy smoker corresponded to the spectra of tobacco condensate and not to the investigated biopsies of graphite peneumoconiosis. RECOMMENDATION AND OUTLOOK: The analyses were performed in order to find out whether mass-spectrometric criteria exist for the differentiation of carbonaceous lung-tissue deposits. Mass spectrometry may be a valuable tool in determining the composition of carbon compounds deposited in human lung tissue. So far, qualitative assessment of the composition of deposits in lung tissue is only possible after the patient is deceased (autopsy).     

Levels of dioxins in fish and fishery products on the German market

In 1995-1998 the contents of polychlorinated dibenzodioxins and dibenzofurans of 184 pooled fish samples were analysed. Sampling focused on fish and fishery products with a market share of more than 1% and covered all fishing grounds important for the supply of the German market. Investigation included 15 different fish species, shrimp, mussel and squid samples and various fishery products, typically on the German market. Generally lean fish species like cod, saithe or Alaska pollock were less contaminated on fresh weight basis than fat fish species like herring, Greenland halibut and sardine. In herring the dioxin content is related to the fishing ground. Low concentrations were found in North Sea herring, high concentrations measured in samples from the Baltic Sea. Dioxin contents in fishery products did not differ significantly from the raw fish samples. Results allow an estimation of the daily intake of dioxins and furans via fish consumption in Germany. Based on a daily fish consumption of 20 g the average intake of dioxins via fish is 6.2 pg WHO-PCDD/F-TEQs per person and day.     

Ethoxyresorufin-O-deethylase (EROD) Activity in Dab (Limanda limanda) as Biomarker for Marine Monitoring (6 pp)

Goal, Scope and Background Ethoxyresorufin-O-deethylase (EROD) is a well-accepted marker for biological effects in fish and is, therefore, part of numerous monitoring programmes. EROD activity was measured in livers of dab (Limanda limanda) from the German Bight (North Sea) from 1995 to 2003. The aim of the present long-term study was (a) time trend monitoring of EROD activity of dab from the German Bight and (b) to elucidate the needs for a successful application of EROD activity as an early warning system. Methods. EROD activities were determined fluorimetrically in dab liver microsomes, using resorufin as an external standard. The limit of detection (LD) and the limit of quantification (LQ) were calculated. Results were referred to protein concentrations. Results and Discussion. EROD activities of 610 female dab caught in different seasons between January 1995 and August 2003 were analyzed individually. Activities varied from 〈 LD to 1768 pmol/(min mg protein) and showed an annual cycle as well as significant differences between the years. Highest EROD activities were observed in early summer and lowest activities during the winter period. In autumn 2002, significantly elevated EROD activities were detected, possibly related to effects of the River Elbe flood event. Two scenarios with different EROD baseline data are presented to discuss the prerequisites for the use of EROD as a monitoring tool. The comparison of these scenarios underlines the importance of appropriate season-specific baseline data. Conclusion. The use of EROD as an early warning tool for contaminant effects in dab in the German Bight has different prospects during the year, because, due to the high background variability, elevated EROD activities are less easy to detect in spring/summer than during the remaining times of the year. Recommendation and Outlook. The availability of site-specific data on the EROD baseline level, its random variation and its annual cycle is a necessary prerequisite for monitoring. If monitoring is to be carried out only for a limited time period of the year, a season with low background variability in EROD activity (autumn) should be chosen to avoid the need for a compensation of the temperature-triggered shift in sexual cycles and the resulting changes in EROD activity.     

Fate of acetone in water

The physical, chemical, and biological processes that might affect the concentration of acetone in water were investigated in laboratory studies. Processes considered included volatilization, adsorption by sediments, photodecomposition, bacterial degradation, and absorption by algae and molds. It was concluded that volatilization and bacterial degradation were the dominant processes determining the fate of acetone in streams and rivers.     

Multiple stressors in amphibian communities: effects of chemical contamination, bullfrogs, and fish.

A leading hypothesis of amphibian population declines is that combinations of multiple stressors contribute to declines. We examined the role that chemical contamination, competition, and predation play singly and in combination in aquatic amphibian communities. We exposed larvae of American toads (Bufo americanus), southern leopard frogs (Rana sphenocephala), and spotted salamanders (Ambystoma maculatum) to overwintered bullfrog tadpoles (R. catesbeiana), bluegill sunfish (Lepomis macrochirus), the insecticide carbaryl, and ammonium nitrate fertilizer in 1000-L mesocosms. Most significantly, our study demonstrated that the presence of multiple factors reduced survival of B. americanus and A. maculatum and lengthened larval periods of R. sphenocephala. The presence of bluegill had the largest impact on the community; it eliminated B. americanus and A. maculatum and reduced the abundance of R. sphenocephala. Chemical contaminants had the second strongest effect on the community with the insecticide, reducing A. maculatum abundance by 50% and increasing the mass of anurans (frogs and toads) at metamorphosis; the fertilizer positively influenced time and mass at metamorphosis for both anurans and A. maculatum. Presence of overwintered bullfrogs reduced mass and increased time to metamorphosis of anurans. While both bluegill and overwintered bullfrog tadpoles had negative effects on the amphibian community, they performed better in the presence of one another and in contaminated habitats. Our results indicate that predicting deleterious combinations from single-factor effects may not be straightforward. Our research supports the hypothesis that combinations of factors can negatively impact some amphibian species and could contribute to population declines.     

Microbial spheres: a novel cyanobacterial–diatom symbiosis

Cyanobacteria, algae and bacteria are widespread inhabitants of North Sea microbial mats. Our studies of these populations showed uncommon modes of living and extraordinary structures, which have not been described before. The structures are spherical objects covering a community of cyanobacteria, diatoms and bacteria. The cultivation of these communities in the laboratory and intensive observations of their exceptional movement has led to some spectacular findings. The sphere formations go through different phases with variation in the dominance of different microorganisms. The role of the bacteria is the most important in the first phase, and can be increased by the addition of signal substances. Spheres surrounded by envelopes of unknown composition and permeability appear, with numerous bacteria and sporadic diatoms inside. Then the cyanobacteria penetrate the spheres and arrange themselves at the surface. The communities proliferate over some weeks and are finally released. Laboratory expositions of the microbial communities to different parameters pinpoint the limits of sphere formation. The metabolic products of the sphere communities are concentrated in the spheres and lead to a different kind of compound compared with the surrounding environment. In this way, the microbial communities strongly influence the structure of the sediments. Uncommon circular structures, which develop into spheres between 0.08 and 3 mm in size were found in subcultures of non-axenic filamentous cyanobacteria enrichments from North Sea microbial mats. These filamentous cyanobacteria (Phormidium sp.) together with associated benthic diatoms of the genus Navicula and associated heterotrophic bacteria were held as reproducible synergistic cultures. Phormidium sp. filaments tightly intertwined with each other, formed the surface of the spheres, trapping diatoms inside. The formation of "spheres" was the result of radial and synchronous movements of the cyanobacteria. In old cultures, the direction of the cyanobacterial movement has turned in the opposite direction, away from the sphere. The integrity of large "spheres" was influenced by chemotactic phenomena and maintained by some type of trichome-trichome interaction. This suggests the presence of metabolic secondary products, which attract cyanobacteria and influence their movement in a form of chemotactic response.     

A Nationwide Analysis of U.S. Army Corps of Engineers Reservoir Performance in Meeting Operational Targets

The United States (U.S.) Army Corps of Engineers operates reservoirs across the U.S. with 89% of reservoirs constructed prior to 1980. Many reservoirs have experienced changes in environmental conditions (e.g., climate and sediment yield) and societal conditions (e.g., water/energy demand and ecological flows) since construction. These changes may challenge the potential for reservoirs to meet their operational targets (OTs) (management goals). Historic daily reservoir data and OTs were collected for 233 reservoirs. Analyses were developed to identify when and where reservoirs may be systematically departing from OTs in terms of the frequency and magnitude of departure. Fifty‐six percent of reservoirs consistently met operating targets, 30% were borderline, and 13% experienced frequent and large magnitude departures. Fifty‐two percent of reservoirs with large departures were due to shortages and were located in the South Pacific and Southwestern divisions. This work provides a framework to identify reservoir performance in relation to management goals, a necessary step for moving toward adaptive management under changing conditions. All individual reservoir analyses are provided via an interactive data visualization tool: https://nicholasinstitute.duke.edu/reservoir-data .