Deactivation of titanium dioxide photocatalyst by oxidation of polydimethylsiloxane and silicon sealant off-gas in a recirculating batch reactor

We have studied deactivation of titanium dioxide (TiO2) photocatalyst by oxidation of polydimethylsiloxane and silicone sealant off-gas in a recirculating batch reactor. Polydimethylsiloxane vapor is a model indoor air pollutant. It does not adsorb strongly on TiO2 in the dark, but undergoes oxidation when the ultraviolet (UV) photons are also present. Commercial silicone (room-temperature vulcanizing) sealant off-gas is an actual indoor air pollutant subject to short-term spikes in concentration. It does adsorb on the TiO2 surface in the dark, but UV photons also catalyze its oxidation. The oxidation of the Si-containing vapors was monitored using a Fourier transform infrared spectroscope equipped with a gas cell. Subsequent to each incremental exposure, a hexane oxidation reaction was performed to track the titania catalyst's activity. The exposures were repeated until substantial deactivation was achieved. We have also documented the regenerative effect of washing the catalyst surface with water. Surface science techniques were used to view the topography of the catalyst and to identify the elements causing the deactivation. Procedural observations of interest in the context of our recirculating batch reactor include the following: the rate of oxidation of hexane was used to assess the activity of a photocatalyst sample; hexane is an appropriate choice of a probe molecule because it does not adsorb in the dark and it undergoes photocatalytic oxidation (PCO) completely, forming CO2; and hexane does not deactivate the photocatalyst surface.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium

A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.     

Essential and non-essential element concentrations in two sleeper shark species collected in arctic waters

A number of elements/metals have increased in arctic biota and are of concern due to their potential toxicity. Most studies on elements in the Arctic have focused on marine mammals and seabirds, but concentrations in the Greenland shark (Somniosus microcephalus) and Pacific sleeper shark (Somniosus pacificus), the only two shark species known to regularly inhabit arctic waters, have never been reported. To address this data gap, concentrations and patterns of 25 elements were analyzed in liver of Greenland sharks collected about Cumberland Sound (n=24) and Pacific sleeper sharks collected about Prince William Sound (n=14). Several non-essential elements differed between species/locations, which could suggest geographical exposure differences or ecological (e.g., diet) differences between the species. Certain essential elements also differed between the two sleeper sharks, which may indicate different physiological requirements between these closely related shark species, although information on such relationships are lacking for sharks and fish.     

Demographic Forecasting in Koala Conservation

Abstract: The koala currently needs conservation intervention. There is clear evidence of decline in many populations, but the existence of other stable or expanding populations offers the possibility of a variety of creative solutions to their conservation problems. The 1998 National Koala Conservation Strategy emphasizes the need to obtain demographic information and to use this information to assess management options for koalas. We need accurate diagnoses of the status of koala populations and forecasts of their demographic future with and without particular management actions. In a qualitative fashion, this process has been undertaken many times on a local and national scale. Quantitative demographic forecasting tools are increasingly available, and koala management could benefit from their application both at the scale of individual populations and more broadly. There is already a considerable body of suitable data on the dispersal, effects of normal and catastrophic environmental variation on reproduction and survival, and on the effects of habitat change. Demographic forecasting, however, is hampered because the full suite of information is rarely available from a single population. In two Queensland populations, retrospective population viability analyses provided forecasts that were in agreement with observed population trends. Work is needed to determine whether data from one population can be applied to other populations. Models can then be developed to make projections at a multipopulation level on the basis of local population dynamics and dispersal. Certain koala populations, because of their long history of study, offer the opportunity to test demographic models retrospectively. These tests will not only aid in fine-tuning the models for koala biology and data but will also assist with the more general process of validating the models.     

Will Observation Error and Biases Ruin the Use of Simple Extinction Models?

Abstract: Estimating the risk of extinction for populations of endangered species is an important component of conservation biology. These estimates must be made from data that contain both environmental noise in the year-to-year transitions in population size (so-called "process error"), random errors in sampling, and possible biases in sampling ( both forms of observation errors). To determine how much faith to place in estimated extinction rates, it is important to know how sensitive they are to observation error. We used three simple, commonly employed models of population dynamics to generate simulated population time series. We then combined random observation error or systematic biases with those data, fit models to the time series data, and observed how close the extinction dynamics of the fitted models compared with the dynamics of the underlying models. We found that systematic biases in sampling rarely affected estimates of extinction risk. We also found that even moderate levels of random observation error do not significantly affect extinction estimates except over a small range of process errors, corresponding to the region where extinction risk is most uncertain. With more substantial sampling error, estimates of extinction risk degraded rapidly. Field census techniques for a variety of taxa often involve observation errors within ±32% of actual population sizes. For typical time series used in conservation, therefore, we often may not need to be overly concerned about observation errors as an extra source of imperfection in our estimated extinction rates.     

An experiment on the ability of free-ranging turkey vultures (Cathartes aura) to locate carrion by chemical cues

((without abstract.))     

The sands of Forvie (Scotland): A case study in geomorphology and conservational management

The Sands of Forvie, National Nature Reserve, Scotland is a complex coastal sand dune system which is associated with the dynamic estuary of the River Ythan. The dune system has developed over more than 5000 years. The south part is a peninsula of dunes, sand hills, sand arcs, erosion and deflation surfaces. The north part is superimposed on a rock plateau with a cliff coastline. This plateau is covered in glacial deposits and is essentially an upland heath landscape. Some of the best examples of large active parabolic dunes in Britain are found in North Forvie. The sequence of geomorphic development is described. As a nature reserve with a rich ecology it has been managed for conservational purposes since 1960s. As such it is an excellent case study of how conservational management has changed to become more flexible and more aware of the importance of dynamic processes.     

Responding to a policy mandate to collaborate: structuring collaboration in the collaborative forest landscape restoration program

The Collaborative Forest Landscape Restoration Program (CFLRP) aims to expand the pace and scale of forest restoration on national forests in the United States. The program requires candidate projects to develop landscape-scale forest restoration proposals through a collaborative process and continue to collaborate throughout planning, implementation, and monitoring. Our comparative case analysis of the initial selected projects examines how existing collaborative groups draw on past experience of collaboration and the requirements of a new mandate to shape collaborative structures as they undertake CFLRP work. While mandating collaboration appears contrary to what is often defined as an informal and emergent process, mandates can encourage stakeholder engagement and renew commitment to overcome past conflict. Our findings also suggest that a collaborative mandate can lead to increased attention and scrutiny, prompting adjustments to collaborative process and structure. As such, mandating collaboration creates dynamic tensions between past experience and new requirements for collaborative practice.