Formation and surface exchange of nitrous acid

Die salpetrige Säure (HONO) ist eine der reaktiven Stickstoffkomponenten der Atmosphäre und Pedosphäre. Die genauen Bildungswege von HONO, sowie der gegenseitige Austausch von HONO zwischen Atmosphäre und Pedosphäre sind noch nicht vollständig aufgedeckt. Bei der HONO-Photolyse entsteht das Hydroxylradikal (OH) und Stickstoffmonooxid (NO), was die Bedeutsamkeit von HONO für die atmosphärische Photochemie widerspiegelt.rnUm die genannte Bildung von HONO im Boden und dessen anschließenden Austausch mit der Atmosphäre zu untersuchen, wurden Messungen von Bodenproben mit dynamischen Kammern durchgeführt. Im Labor gemessene Emissionsflüsse von Wasser, NO und HONO zeigen, dass die Emission von HONO in vergleichbarem Umfang und im gleichen Bodenfeuchtebereich wie die für NO (von 6.5 bis 56.0 % WHC) stattfindet. Die Höhe der HONO-Emissionsflüsse bei neutralen bis basischen pH-Werten und die Aktivierungsenergie der HONO-Emissionsflüsse führen zu der Annahme, dass die mikrobielle Nitrifikation die Hauptquelle für die HONO-Emission darstellt. Inhibierungsexperimente mit einer Bodenprobe und die Messung einer Reinkultur von Nitrosomonas europaea bestärkten diese Theorie. Als Schlussfolgerung wurde das konzeptionelle Model der Bodenemission verschiedener Stickstoffkomponenten in Abhängigkeit von dem Wasserhaushalt des Bodens für HONO erweitert.rnIn einem weiteren Versuch wurde zum Spülen der dynamischen Kammer Luft mit erhöhtem Mischungsverhältnis von HONO verwendet. Die Messung einer hervorragend charakterisierten Bodenprobe zeigte bidirektionale Flüsse von HONO. Somit können Böden nicht nur als HONO-Quelle, sondern auch je nach Bedingungen als effektive Senke dienen. rnAußerdem konnte gezeigt werden, dass das Verhältnis von HONO- zu NO-Emissionen mit dem pH-Wert des Bodens korreliert. Grund könnte die erhöhte Reaktivität von HONO bei niedrigem pH-Wert und die längere Aufenthaltsdauer von HONO verursacht durch reduzierte Gasdiffusion im Bodenporenraum sein, da ein niedriger pH-Wert mit erhöhter Bodenfeuchte am Maximum der Emission einhergeht. Es konnte gezeigt werden, dass die effektive Diffusion von Gasen im Bodenporenraum und die effektive Diffusion von Ionen in der Bodenlösung die HONO-Produktion und den Austausch von HONO mit der Atmosphäre begrenzen. rnErgänzend zu den Messungen im Labor wurde HONO während der Messkampagne HUMPPA-COPEC 2010 im borealen Nadelwald simultan in der Höhe von 1 m über dem Boden und 2 bis 3 m über dem Blätterdach gemessen. Die Budgetberechnungen für HONO zeigen, dass für HONO sämtliche bekannte Quellen und Senken in Bezug auf die übermächtige HONO-Photolyserate tagsüber vernachlässigbar sind (< 20%). Weder Bodenemissionen von HONO, noch die Photolyse von an Oberflächen adsorbierter Salpetersäure können die fehlende Quelle erklären. Die lichtinduzierte Reduktion von Stickstoffdioxid (NO2) an Oberflächen konnte nicht ausgeschlossen werden. Es zeigte sich jedoch, dass die fehlende Quelle stärker mit der HONO-Photolyserate korreliert als mit der entsprechenden Photolysefrequenz, die proportional zur Photolysefrequenz von NO2 ist. Somit lässt sich schlussfolgern, dass entweder die Photolyserate von HONO überschätzt wird oder dass immer noch eine unbekannte, HONO-Quelle existiert, die mit der Photolyserate sehr stark korreliert. rn rn

Geochemistry and Stable Isotopes of Surface Water and Groundwater in the Continental Pit in Butte, Montana, USA

The Continental porphyry Cu‐Mo mine, located 2 km east of the famous Berkeley Pit lake of Butte, Montana, contains two small lakes that vary in size depending on mining activity. In contrast to the acidic Berkeley Pit lake, the Continental Pit waters have near-neutral pH and relatively low metal concentrations. The main reason is geological: whereas the Berkeley Pit mined highly‐altered granite rich in pyrite with no neutralizing potential, the Continental Pit is mining weakly‐altered granite with lower pyrite concentrations and up to 1‐2% hydrothermal calcite. The purpose of this study was to gather and interpret information that bears on the chemistry of surface water and groundwater in the active Continental Pit. Pre‐existing chemistry data from sampling of the Continental Pit were compiled from the Montana Bureau of Mines and Geology and Montana Department of Environmental Quality records. In addition, in March of 2013, new water samples were collected from the mine’s main dewatering well, the Sarsfield well, and a nearby acidic seep (Pavilion Seep) and analyzed for trace metals and several stable isotopes, including dD and d18O of water, d13C of dissolved inorganic carbon, and d34S of dissolved sulfate. In December 2013, several soil samples were collected from the shore of the frozen pit lake and surrounding area. The soil samples were analyzed using X‐ray diffraction to determine mineral content. Based on Visual Minteq modeling, water in the Continental Pit lake is near equilibrium with a number of carbonate, sulfate, and molybdate minerals, including calcite, dolomite, rhodochrosite (MnCO3), brochantite (CuSO4·3Cu(OH)2), malachite (Cu2CO3(OH)2), hydrozincite (Zn5(CO3)2(OH)6), gypsum, and powellite (CaMoO4). The fact that these minerals are close to equilibrium suggests that they are present on the weathered mine walls and/or in the sediment of the surface water ponds. X‐Ray Diffraction (XRD) analysis of the pond “beach” sample failed to show any discrete metal‐bearing phases. One of the soil samples collected higher in the mine, near an area of active weathering of chalcocite‐rich ore, contained over 50% chalcanthite (CuSO4·5H2O). This water‐soluble copper salt is easily dissolved in water, and is probably a major source of copper to the pond and underlying groundwater system. However, concentrations of copper in the latter are probably controlled by other, less‐soluble minerals, such as brochantite or malachite. Although the acidity of the Pavilion Seep is high (~ 11 meq/L), the flow is much less than the Sarsfield Well at the current time. Thus, the pH, major and minor element chemistry in the Continental Pit lakes are buffered by calcite and other carbonate minerals. For the Continental Pit waters to become acidic, the influx of acidic seepage (e.g., Pavilion Seep) would need to increase substantially over its present volume.

Physiological responses of the marine diatom Thalassiosira pseudonana to increased pCO2 and seawater acidity

We studied the effects of elevated CO2 concentration and seawater acidity on inorganic carbon acquisition, photoinhibition and photoprotection as well as growth and respiration in the marine diatom Thalassiosira pseudonana. After having grown under the elevated CO2 level (1000 µatm, pH 7.83) at sub-saturating photosynthetically active radiation (PAR, 75 µmol photons/m**2/s) for 20 generations, photosynthesis and dark respiration of the alga increased by 25% (14.69 ± 2.55 fmol C/cell/h) and by 35% (4.42 ± 0.98 fmol O2/cell/h), respectively, compared to that grown under the ambient CO2 level (390 µatm, pH 8.16), leading to insignificant effects on growth (1.09 ± 0.08 (1/d))v 1.04 ± 0.07 (1/d)). The photosynthetic affinity for CO2 was lowered in the high-CO2 grown cells, reflecting a down-regulation of the CO2 concentrating mechanism (CCM). When exposed to an excessively high level of PAR, photochemical and non-photochemical quenching responded similarly in the low- and high-CO2 grown cells, reflecting that photoinhibition was not influenced by the enriched level of CO2. In T. pseudonana, it appeared that the energy saved due to the down-regulated CCM did not contribute to any additional light stress as previously found in another diatom Phaeodactylum tricornutum, indicating differential physiological responses to ocean acidification between these two diatom species.

Annual crop rotation of tropical pastures with no-till soil as affectedby lime surface application.

Soil acidity and low natural fertility are the main limiting factors for grain production in tropical regionssuch as the Brazilian Cerrado. The application of lime to the surface of no-till soil can improve plant nutrition, dry matter production, crop yields and revenue. The present study, conducted at the Lageado Experimental Farm in Botucatu, State of São Paulo, Brazil, is part of an ongoing research project initi-ated in 2002 to evaluate the long-term effects of the surface application of lime on the soil?s chemical attributes, nutrition and kernel/grain yield of peanut (Arachis hypogaea), white oat (Avena sativa L.) and maize (Zea mays L.) inter cropped with palisade grass (Urochloa brizantha cv. Marandu), as well as the forage dry matter yield of palisade grass in winter/spring, its crude protein concentration, estimated meat production, and revenue in a tropical region with a dry winter during four growing seasons. The experiment was designed in randomized blocks with four replications. The treatments consisted of four rates of lime application (0, 1000, 2000 and 4000 kg ha−1), performed in November 2004. The surface application of limestone to the studied tropical no-till soil was efficient in reducing soil acidity from the surface down to a depth of 0.60 m and resulted in greater availability of P and K at the soil surface. Ca and Mg availability in the soil also increased with the lime application rate, up to a depth of 0.60 m. Nutrient absorption was enhanced with liming, especially regarding the nutrient uptake of K, Ca and Mg by plants.Significant increases in the yield components and kernel/grain yields of peanut, white oat and maize were obtained through the surface application of limestone. The lime rates estimated to achieve the maximum grain yield, especially in white oat and maize, were very close to the rates necessary to increase the base saturation of a soil sample collected at a depth of 0?0.20 m to 70%, indicating that the surface liming of 2000 kg ha−1is effective for the studied tropical no-till soil. This lime rate also increases the forage dry matter yield, crude protein concentration and estimated meat production during winter/spring in the maize-palisade grass inter cropping, provides the highest total and mean net profit during the four growing seasons, and can improve the long-term sustainability of tropical agriculture in the Brazilian Cerrado.

Effect of surface conditions on flow of a micropolar fluid driven by a porous stretching sheet

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Some surface profiles of a strip after plane-strain indentation by rigid bodies with serrated surfaces

This paper is concerned with the surface profiles of a strip after rigid bodies with serrated (saw-teeth) surfaces indent the strip and are subsequently removed. Plane-strain conditions are assumed. This has application in roughness transfer of final metal forming process. The effects of the semi-angle of the teeth, the depth of indentation and the friction on the contact surface on the profile are considered.