Determination of chemical warfare agents

Chlorovinylannes (Lewisites) were produced and handled during WW I and WW II as chemical warfare agents. Residues of these cwa and their metabolites are still present today and continue to contaminate soil and water. A gas Chromatographic method for the detection and determination of chlorovinylarsines (Lewisites) and their metabolites is shown. Lewisite II and Lewisite III, but not Lewisite I and the metabolites of Lewisite I and Lewisite II can be detected and determined using GC/ECD. After derivatization with thiols, the sum of Lewisite I or Lewisite II and their metabolites are detected. With the proper selection of the thiol, matrix interferences can be eliminated because of the different retention times of the derivatives.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

Housing growth,forests, and public lands in Northern Wisconsin from 1940 to 2000

Rural, forested areas throughout the United States are experiencing strong housing growth with potentially detrimental impacts on the environment. In this paper, we quantify housing growth in Northern Wisconsin over the last sixty years to determine if growth rates were higher near public lands, which may represent an important recreational amenity. We used data from the U.S. Census to produce decadal housing density estimates, “backcasts,” from 1940 to 2000 for northern Wisconsin to examine “rural sprawl” in northern Wisconsin and its relationship to forested areas and public lands. We integrated housing density estimates with the 1992/1993 National Land Cover Dataset to examine the relationship between rural sprawl and land cover, especially forests. Between 1940 and 2000, private land with <2 housing units/km² decreased from 47% to 21% of the total landscape. Most importantly, housing growth was concentrated along the boundaries of public lands. In 14 of the 19 counties that we studied, housing growth rates within 1 km of a public land boundary exceeded growth rates in the remainder of the county, and three of the five counties that did not exhibit this pattern, were the ones with the least amount of public land. Future growth can be expected in areas with abundant natural amenities, highlighting the critical need for additional research and effective natural resource management and regional planning to address these challenges.     

Root exudation, phosphorus acquisition, and microbial diversity in the rhizosphere of white lupine as affected by phosphorus supply and atmospheric carbon dioxide concentration

White lupine (Lupinus albus L.) was used as a phosphorus (P)-efficient model plant to study the effects of elevated atmospheric CO(2) concentrations on (i) P acquisition, (ii) the related alterations in root development and rhizosphere chemistry, and (iii) the functional and structural diversity of rhizosphere microbial communities, on a P-deficient calcareous subsoil with and without soluble P fertilization. In both +P (80 mg P kg(-1)) and -P treatments (no added P), elevated CO(2) (800 micromol mol(-1)) increased shoot biomass production by 20 to 35% and accelerated the development of cluster roots, which exhibit important functions in chemical mobilization of sparingly soluble soil P sources. Accordingly, cluster root formation was stimulated in plants without P application by 140 and 60% for ambient and elevated CO(2) treatments, respectively. Intense accumulation of citrate and increased activities of acid and alkaline phosphatases, but also of chitinase, in the rhizosphere were mainly confined to later stages of cluster root development in -P treatments. Regardless of atmospheric CO(2) concentrations, there was no significant effect on accumulation of citrate or on selected enzyme activities of C, N, and P cycles in the rhizosphere of individual root clusters. Discriminant analysis of selected enzyme activities revealed that mainly phosphatase and chitinase contributed to the experimental variance (81.3%) of the data. Phosphatase and chitinase activities in the rhizosphere might be dominated by the secretion from cluster roots rather than by microbial activity. Alterations in rhizosphere bacterial communities analyzed by denaturing gradient gel electrophoresis (DGGE) were related with the intense changes in root secretory activity observed during cluster root development but not with elevated CO(2) concentrations.     

Influence of fish on habitat choice of water birds: a whole system experiment

It is notoriously difficult to study population interactions among highly mobile animals that cannot be meaningfully confined to experimental plots of limited size. For example, migratory water birds are believed to suffer from competition with resident fish populations for shared food resources. While observational evidence in support of this hypothesis is accumulating, replicated experiments addressing this issue at the proper spatial scale are lacking. Here, we report from a replicated whole-system experiment in which we stocked large (0.07 km2), shallow (< or =2.5 m deep), highly eutrophic ponds in the bird protection area "Ismaninger Speichersee mit Fischteichen" with different densities of carp and assessed the responses of water birds and their food resources during summer over several years. In all years, the biomasses of benthic macroinvertebrates, macroalgae, and macrophytes as well as the densities of herbivorous, carnivorous, and omnivorous water birds were reduced in carp ponds compared to fishless ponds. The negative effects of carp on food resources and on the numbers of water birds feeding in carp ponds increased over the season (May-September) and were stronger at high than at low stocking densities of carp. Consequently, differences in resource densities between ponds with and without carp increased, and the ranking of ponds with respect to resource densities became more predictable over the season. These factors may have contributed to a seasonal improvement of the birds' abilities to track resource densities across ponds, as suggested by tight correlations of bird numbers on ponds with resource densities late, but not early, in the season.     

Increasing development in the surroundings of U.S. National Park Service holdings jeopardizes park effectiveness

Protected areas are cornerstones of biodiversity conservation, but they are in danger of becoming islands in a sea of human dominated landscapes. Our question was if protected areas may even foster development in their surroundings because they provide amenities that attract development, thus causing the isolation of the ecosystems they were designed to protect. Our study analyzed historic aerial photographs and topographical maps to reconstruct road development and building growth within and around Indiana Dunes and Pictured Rocks National Lakeshores in the U.S. Great Lakes region from 1938 to 2005, and to estimate the effects of park creation in 1966 on changes in landscape patterns. Historic U.S. census housing density data were used as a baseline to compare observed changes to. Our results showed that park establishment was effective in reducing and stopping the fragmenting impact of development within park boundaries. However, increased amenity levels following park establishment led to enhanced development in the surroundings of both parks. In the extreme case of Indiana Dunes, building density outside the park increased from 45 to 200 buildings/km² and road density almost doubled from 3.6 to 6.6 km/km² from 1938 to 2005. Development rates of change were much higher than in the broader landscape, particularly after park establishment. The potential amenity effect was up to 9500 new buildings in the 3.2-km zone around Indiana Dunes between 1966 and 2005. For Pictured Rocks the absolute effect was smaller but up to 70% of the observed building growth was potentially due to amenity effects. Our findings highlight the need for conservation planning at broader scales, incorporating areas beyond the boundaries of protected areas.     

Ignition of dust-air atmospheres by ultrasonic waves

This paper shows the results of our investigations on the ignition source ultrasound in dust-air atmospheres. Ultrasound is, on the one hand, considered to be an ignition source according to international safety standards (EN 1127–1 (2011)). On the other hand, though, ultrasound is used for various applications in gases and air, such as level and flow measurement, or in the process industry, but no explosion accidents have yet been reported. Our research now shows that it is indeed possible to ignite dust-air mixtures in ultrasound fields under certain conditions. We conducted our experiments in an ultrasound standing wave field and used maize starch, calcium stearate and sulfur dust. For ignitions, an absorbing target was needed to convert the acoustic energy into heat. From theoretical estimations and experiments critical conditions that provoke ultrasonically triggered explosions are identified.