Nitrate reduction in the presence of wüstite

Recent strategies to reduce elevated nitrate concentrations employ metallic Fe0 as a reductant. Secondary products of Fe0 corrosion include magnetite (Fe3O4), green rust [Fe6(OH)12SO4], and wüstite [FeO(s)]. To our knowledge, no studies have been reported on the reactivity of NO3- with FeO(s). This project was initiated to evaluate the reactivity of FeO(s) with NO3- under abiotic conditions. Stirred batch reactions were performed in an anaerobic chamber over a range of pH values (5.45, 6.45, and 7.45), initial FeO(s) concentrations (1, 5, and 10 g L(-1)), initial NO3- concentrations (1, 10, and 15 mM), and temperatures (3, 21, 31, and 41 degrees C) for kinetic and thermodynamic determinations. Suspensions were periodically removed and filtered to measure dissolved nitrogen and iron species. Solid phases were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nitrate reduction by FeO was rapid and characterized by nearly stoichiometric conversion of NO3- to NH4+. Transient NO2- formation also occurred. The XRD and SEM results indicated the formation of Fe3O4 as a reaction product of the heterogeneous redox reaction. Kinetics of NO3- reduction suggested a rate equation of the type: -d[NO3-]/dt = k[FeO]0.57[H]0.22[NO3-]1.12 where k = 3.46 x 10(-3) +/- 0.38 x 10(-3) M(-1) s(-1), at 25 degrees C. Arrhenius and Eyring plots indicate that the reaction is surface chemical-controlled and proceeds by an associative mechanism involving a step where both NO3- and FeO(s) bind together in an intermediate complex.     

An Innovative Index for Evaluating Water Quality in Streams

A water quality index expressed as a single number is developed to describe overall water quality conditions using multiple water quality variables. The index consists of water quality variables: dissolved oxygen, specific conductivity, turbidity, total phosphorus, and fecal coliform. The objectives of this study were to describe the preexisting indices and to define a new water quality index that has advantages over these indices. The new index was applied to the Big Lost River Watershed in Idaho, and the results gave a quantitative picture for the water quality situation. If the new water quality index for the impaired water is less than a certain number, remediation—likely in the form of total maximum daily loads or changing the management practices—may be needed. The index can be used to assess water quality for general beneficial uses. Nevertheless, the index cannot be used in making regulatory decisions, indicate water quality for specific beneficial uses, or indicate contamination from trace metals, organic contaminants, and toxic substances.     

Feasibility and costs of phosphorus application limits on 39 U.S. swine operations

Concerns about manure P and water quality have prompted new regulations imposing P limits on land application of manure. Previous research established that P limits increase land needs for animal feeding operations. We evaluated the effect of N, annual P, and rotation P limits on the feasibility of manure management. A mechanistic model characterized manure management practices on 39 swine operations (20 unagitated lagoon and 19 slurry operations) in five states (Iowa, Missouri, North Carolina, Oklahoma, and Pennsylvania). Extensive information collected from each operation was used to determine effects of manure storage type, ownership structure, and application limits on attributes of manure management. Phosphorus limits had substantially greater effect on slurry operations, increasing land needs 250% (0.3 hectares per animal unit [AU]) and time for manure application 24% (2.5 min AU(-1)) for rotation P limits and 41% (4.4 min AU(-1)) for annual P limits. Annual P limits were infeasible for current land application equipment on two operations and had the greatest effect on time and costs because they required all but three slurry operations to reduce discharge rate. We recommend implementing rotation P limits (not to exceed crop N need) to minimize time effects, allow most farmers to use their current manure application methods, and allow manure to fulfill crop N and P needs in the year of application. Phosphorus limits increased potential manure value but would require slurry operations to recover at least 61% of manure value through manure sales. Phosphorus limits are likely to shape the U.S. swine industry through differential effects on the various sectors of the swine industry.     

The oldest European fossil songbird from the early Oligocene of Germany

We report on the oldest European songbird (Passeriformes), from the early Oligocene (30–34 million years ago) of Frauenweiler in Germany. The specimen represents the earliest associated remains of an early Tertiary passerine described so far. It ties the first appearance of Passeriformes in Europe to a minimum age of 30 million years. Passeriform birds are absent in Eocene deposits that yielded abundant remains of small land birds and apparently dispersed into Europe around the Eocene/Oligocene boundary (about 34 million years ago), not at the Oligocene/Miocene boundary (about 24 mya) as hitherto thought. This possibly relates the appearance of songbirds in Europe to a well-known major faunistic break at the Eocene/Oligocene boundary, called the grande coupure. The Frauenweiler songbird most notably differs from extant Passeriformes in having a larger processus procoracoideus on the coracoid and appears to be outside Eupasseres, the taxon which includes Oscines (all modern European and most Old World songbirds) and Suboscines (most South and Central American songbirds). It shows that there were earlier dispersal events of non-oscine songbirds into Europe before the arrival of Oscines from the Australian continental plate towards the late Oligocene.     

Low Levels of Sodium and Potassium in the Water from Wetlands in Minnesota that Contained Malformed Frogs Affect the Rate of Xenopus Development

Water samples were collected between 1999 and 2000 from wetlands in Minnesota that contained malformed frogs. The water samples were analyzed for 14 minerals/ions and screened for the presence of biologically active compounds using Xenopus laevis. Results indicated that water from two sites, CWB and ROI2, induced severe retardation with embryo lengths reduced 20% after 96 hr of development. The developmental delay observed with water from ROI2 was alleviated by supplementation with sodium, while both sodium and potassium alleviated the developmental delay observed with water whose mineral content mimicked that of CWB. Seasonal fluctuations in the sodium and potassium content at ROI2 and NEY correlated with changes in the rates of Xenopus development. Xenopus embryos reared on water from ROI2 for 120 hr displayed gut malformations not present in embryos reared on a synthetic media designed to mimic the mineral content of the water from ROI2. Embryos reared on water from ROI2 supplemented with minerals at levels comparable to that routinely employed in the rearing of Xenopus were neither retarded nor malformed. It is proposed that climate driven hydrology may influence the mineral composition at selected wetlands and delay development which may alter window(s) of susceptibility towards biologically active agents and the occurrence of malformed frogs.     

A multi media load model for the Baltic Sea

The background of this work is the international decision process with regard to the selection of chemicals to be assessed with priority. In order to stress the precautionary principle, mass flows were analysed rather than concentrations, threshold values, etc., as preferred by the chemical legislation (which still excludes the marine area). Lindane, hexachlorobenzene (HCB), trichloroacetic acid and its sodium salt, medium-chained chlorinated paraffins and tributyltin (TBT) were selected due to their great relevance for the marine area. Trichloroacetic acid is an interesting model compound on account of its accidental formation by degradation of volatile chlorinated hydrocarbons and during chlorination processes. In addition, a hypothetical compound was modelled, representing a highly water-soluble substance with low vapour pressure. The balancing area is the Baltic Sea and its catchment area. In order to model the substance flows, the 'Input/Output-load model' has been developed. The model quantifies the shift and the distribution of a yearly load of the substance investigated from the terrestrial-limnic into the marine compartment (Baltic Sea). Water-soluble substances, which are usually considered to be of no concern, may enter the sea in great amounts and, if not degradable, remain there. It turned out to be necessary to take into account remobilisation, unintended formation and point as well as line-sources.     

Zur Methylierung von 1-Phenyl-5-sulfanilamido-pyrazol

The Science of Nature -     

Correlations between Human Collecting and Intertidal Mollusc Populations on Rocky Shores

We tested whether the population structures of intertidal molluscs varied with the activity of human collectors in northern Port Phillip Bay, Victora, Australia. We examined eight sites, two of which had been protected for around 70 years by the area being used as a rifle range with the other six being visited frequently by human. The shores were examined in two different years, and in 1991 we counted humans and recorded their activities. At heavily visited shores, almost half of the people seen were simply walking, while 25% were actively collecting, despite regulations prohibiting the collection of intertidal gastritis. The remaining people were fishing or skydiving. At the protected shores, we observed only one collector and a handful of walkers over more than 20 observation periods, including weekdays, normal weekends, and holiday weekends. In 1989 and 1991, we compared size distributions of seven intertidal species between sites in the two categories. Four mollify species are taken for food and bait; the remaining three served as “controls”. The size distributions and abundance of noncarbonated species (alicized napalm, Leaderless viola, and emization ebonies) did not differ between visited and protected sites in either year, although most species did vary between individual sites. In contrast, three of the four collected species, alicize trampoliners, Austrocochlea constricta, and Nerita atramentosa, were significantly larger at the protected sites, and N. atramentosa was markedly less abundant at heavily visited sites. The fourth collected species, Turbo undulatus, has a distribution extending into the subtidal zone, and it is possible that intertidal populations ate replenished from deeper water. The changes in mean size of molluscs are well within the range reported from South America and South Africa under subsistence fishing, and they demonstrate that at least close to major urban centers, human recreational activities can have substantial effects in developed countries.