Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

Cache and carry: hoarding behavior of arctic fox

Food-hoarding animals are expected to preferentially cache items with lower perishability and/or higher consumption time. We observed arctic foxes (Alopex lagopus) foraging in a greater snow goose (Anser caerulescens atlanticus) colony where the main prey of foxes consisted of goose eggs, goslings, and lemmings (Lemmus and Dicrostonyx spp.). We recorded the number of prey consumed and cached and the time that foxes invested in these activities. Foxes took more time to consume a goose egg than a lemming or gosling but cached a greater proportion of eggs than the other prey type. This may be caused by the eggshell, which presumably decreases the perishability and/or pilfering risk of cached eggs, but also increases egg consumption time. Arctic foxes usually recached goose eggs but rarely recached goslings or lemmings. We tested whether the rapid-sequestering hypothesis could explain this recaching behavior. According to this hypothesis, arctic foxes may adopt a two-stage strategy allowing both to maximize egg acquisition rate in an undefended nest and subsequently secure eggs in potentially safer sites. Foxes spent more time carrying an egg and traveled greater distances when establishing a secondary than a primary cache. To gain further information on the location and subsequent fate of cached eggs, we used dummy eggs containing radio transmitters. Lifespan of primary caches increased with distance from the goose nest. Secondary caches were generally located farther from the nest and had a longer lifespan than primary caches. Behavioral observations and the radio-tagged egg technique both gave results supporting the rapid-sequestering hypothesis.     

A Model for Landscape Planning Under Complex Spatial Conditions

We present a new mathematical programming framework that is adaptable to a variety of spatially explicit landscape problems in environmental investment, conservation, and land-use planning, transport planning, and agriculture. As part of capturing spatial interdependencies, the framework considers decision variables at two levels, finely spaced grid cells and landholdings. We applied the framework to an environmental investment problem using objective functions representing biodiversity and carbon sequestration. We also tested the model to optimize the path of a road through part of the landscape. Using the Nambucca case study in eastern Australia, we applied a hybrid greedy randomised adaptive search procedure (GRASP) to find solutions to the model.     

Ink utilization by mesopelagic squid

Remotely operated vehicle dive video recordings of deep-sea squid ink release were examined to determine species, ink release type, release depth, and accompanying behavior/s. Ink release was commonly observed between the surface and 1,842.1 m in Monterey Bay, CA, and surrounding waters. Six ink release types were observed: pseudomorphs, pseudomorph series, ink ropes, clouds/smokescreens, diffuse puffs and mantle fills. Each species released ink throughout all or most of its depth range; inking was not limited to shallow, sunlit waters. Individuals of each species produced one ink release type more commonly than other types, however, multiple ink types could be released by individuals of all species. Common behaviors preceded and/or followed each release type; pseudomorphs and pseudomorph series were generally associated with escape behaviors, while ink ropes, clouds, and puffs normally involved the animal remaining adjacent to or amid the ink. Deep-sea squids may use ink for defensive purposes similar to those of shallow-dwelling species when they release pseudomorphs, pseudomorph series, or large clouds, and may use ink puffs in intra-specific communication. The function of ink ropes and mantle fills is unknown.     

Main results of strategic noise maps and action plans in Navarre (Spain)

According to Directive 2002/49, strategic noise maps and their correspondent action plans were carried out in the Autonomous Community of Navarre, Spain. Six strategic noise maps were produced for 120 km of major roads as well as a strategic noise map for the Agglomeration of the Region of Pamplona (ARP) with a population of 280,199 inhabitants. In the ARP, a total of 36,400 people (13.0 %) are exposed to Ln levels over 55 dBA and 42,300 people (15.1 %) are exposed to Lden levels over 65 dBA. With regard to major roads, a total of 3,900 people are exposed to Ln levels over 55 dBA and 2,400 people are exposed to Lden levels over 65 dBA. When designing action plans, different prioritisation criteria concerning rank-based effectiveness measures (mainly the amount of people benefitting from them) were taken into account.     

Contribution of transition metals in the reactive oxygen species activity of PM emissions from retrofitted heavy-duty vehicles

We assessed the contribution of water-soluble transition metals to the reactive oxygen species (ROS) activity of diesel exhaust particles (DEPs) from four heavy-duty vehicles in five retrofitted configurations (V-SCRT, Z-SCRT, DPX, hybrid, and school bus). A heavy-duty truck without any control device served as the baseline vehicle. Particles were collected from all vehicle-configurations on a chassis dynamometer under three driving conditions: cruise (80 km h^?1), transient UDDS, and idle. A sensitive macrophage-based in vitro assay was used to determine the ROS activity of collected particles. The contribution of water-soluble transition metals in the measured activity was quantified by their removal using a Chelex^® complexation method. The study demonstrates that despite an increase in the intrinsic ROS activity (per mass basis) of exhaust PM with use of most control technologies, the overall ROS activity (expressed per km or per h) was substantially reduced for retrofitted configurations compared to the baseline vehicle. Chelex treatment of DEPs water extracts removed a substantial (≥70%) and fairly consistent fraction of the ROS activity, which ascertains the dominant role of water-soluble metals in PM-induced cellular oxidative stress. However, relatively lower removal of the activity in few vehicle-configurations (V-SCRT, DPX and school bus idle), despite a large aggregate metals removal, indicated that not all species were associated with the measured activity. A univariate regression analysis identified several transition metals (Fe, Cr, Co and Mn) as significantly correlated (R > 0.60; p < 0.05) with the ROS activity. Multivariate linear regression model incorporating Fe, Cr and Co explained 90% of variability in ROS levels, with Fe accounting for the highest (84%) fraction of the variance.     

Comparison of methods for evaluation of activity of photocatalytic films

Objective

This work aims to investigate the correlation between the photocatalytic activity determined by methylene blue bleaching (DIN 52980), stearic acid degradation, and degradation of acetone in gas phase.

Method

The photocatalytic TiO₂ coatings included in this investigation ranged from thin commercially available coatings (Activ^TM and BioClean^TM) and ready to use suspensions (Nano-X PK1245) to lab-produced PVD and sol?Cgel coatings. XRD analysis of the photocatalytic coatings showed that all the coatings consisted of nanocrystalline anatase, although the thickness and porosity varied considerably.

Results

The study showed that the reproducibility of the activity measurements was good. However, more importantly, the investigation showed that there is a good correlation between the activities determined by the different methods even though the characteristics of the photocatalytic coatings and the organic probe molecules varied considerably.

Conclusion

The overall findings of this work suggest that there is a good correlation between the investigated methods. These results are promising for the future work concerning standardization of methods for determination of the activity of photocatalytic films.     

Factors diminishing the effectiveness of phosphorus loading from municipal effluent: critical information for TMDL analyses

Factors that diminish the effectiveness of phosphorus inputs from a municipal wastewater treatment facility (Metro) in contributing to phosphorus levels and its availability to support algae growth in a culturally eutrophic urban lake (Onondaga Lake, NY) were characterized and quantified. These factors included the bioavailability and settling characteristics of particulate phosphorus from this effluent, the dominant form (70%) of phosphorus in this input, and the plunging of the discharge to stratified layers in the lake. Supporting studies included: (1) chemical and morphometric characterization of the phosphorus-enriched particles of this effluent, compared to particle populations of the tributaries and lake, with an individual particle analysis technique; (2) conduct of algal bioavailability assays of the particulate phosphorus of the effluent; (3) conduct of multiple size class settling velocity measurements on effluent particles; and (4) determinations of the propensity of the discharge to plunge, and documentation of plunging through three-dimensional monitoring of a tracer adjoining the outfall. All of these diminishing effects were found to be operative for the Metro effluent in Onondaga Lake and will be integrated into a forthcoming phosphorus "total maximum daily load" analysis for the lake, through appropriate representation in a supporting mechanistic water quality model. The particulate phosphorus in the effluent was associated entirely with Fe-rich particles formed in the phosphorus treatment process. These particles did not contribute to concentrations in pelagic portions of the lake, due to local deposition associated with their large size. Moreover, this particulate phosphorus was found to be nearly entirely unavailable to support algae growth. While substantial differences are to be expected for various inputs, the effective loading concept and the approaches adopted here to assess the diminishing factors are broadly applicable.     

Assessing the risk posed by high-turbidity water to water supplies

The objective of this study is to assess the risk of insufficient water supply posed by high-turbidity water. Several phenomena can pose risks to the sufficiency of a water supply; this study concerns risks to water treatment plants from particular properties of rainfall and raw water turbidity. High-turbidity water can impede water treatment plant operations; rainfall properties can influence the degree of soil erosion. Thus, water turbidity relates to rainfall characteristics. Exceedance probabilities are presented for different rainfall intensities and turbidities of water. When the turbidity of raw water is higher than 5,000 NTU, it can cause operational problems for a water treatment plant. Calculations show that the turbidity of raw water at the Ban-Sin water treatment plant will be higher than 5,000 NTU if the rainfall intensity is larger than 165 mm/day. The exceedance probability of high turbidity (turbidity >5,000 NTU) in the Ban-Sin water treatment plant is larger than 10%. When any water treatment plant cannot work regularly, its ability to supply water to its customers is at risk.