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  • Articles  (222)
  • kinetics  (134)
  • nitrogen
  • Springer  (222)
  • Periodicals Archive Online (PAO)
  • Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics  (123)
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  • Articles  (222)
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  • 1
    ISSN: 1572-8862
    Keywords: acetylene ion ; complex ; hydrogen ; nitrogen ; argon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The complexes formed by the positive acetylene ion with the hydrogen molecule, the nitrogen molecule, and the argon atom are investigated with ab initio calculations using the 6-311G** and the 6-31+G(2df,2pd) basis sets. MP2/6-311G** energies and optimum geometries are obtained, as well as single-point MP3, MP4, and QCISD(T) energies with the MP2/6-311G** optimized geometries. Single-point calculations are performed with the 6-31+G(2df,2pd) basis set at MP2/6-311G** optimized geometries.
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  • 2
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    Plasma chemistry and plasma processing 20 (2000), S. 87-110 
    ISSN: 1572-8986
    Keywords: striations ; nitrogen ; spherical discharge ; spatially inhomogeneous Boltzmann equation ; electron velocity distribution function ; dc glow discharge
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Recent observations of spherical striations in large-volume nitrogen dcdischarges with a central anode have stimulated investigations of thenonlocal electron kinetics in these striations by solving the spatiallyinhomogeneous Boltzmann equation adapted to spherical geometry. Becausethe radial course of the electric potential is largely unknown in thisdischarge, different models concerning its radial course have been developedand used. These models are based on the measured radii of the striationsand the assumption that the potential drop between successive striationsdoes not change. As a consequence, with decreasing distance between thestriations the electric field strongly increases toward the centralanode. It has been found that spherical striations are only obtained ifthe electric field is strongly modulated. In this case, a highly nonlocalbehavior of the velocity distribution function and strongly modulatedradial courses of the macroscopic quantities have been obtained.
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  • 3
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    Journal of materials synthesis and processing 8 (2000), S. 139-144 
    ISSN: 1573-4870
    Keywords: TiO2 ; phase transformations ; mechanical alloying ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A high-pressure and high-temperature phase of TiO2 : TiO2 II is formed transiently during room-temperature high-energy ball milling of anatase TiO2 : TiO2 anatase → TiO2 II → TiO2 rutile. Rutile is the only phase present after prolonged ball milling. The present paper focuses on the influences of physical and chemical processing conditions on the transformation kinetics. The effects of two milling parameters on the kinetics of phase transformation of anatase TiO2 were investigated: the nature of milling tools and the powder-to-ball weight ratio R. Granulometric characterizations and TEM observations have demonstrated that the transformation of TiO2 anatase into TiO2 II occurs without fracturing of particles and that TiO2 II nanograins form at the surface of anatase particles. The parameter R affects only the transformation rate. For a given R, the transformation rate is the largest with alumina grinding tools, intermediate with zirconia tools, and the smallest with steel tools. The parameters involved in current models of the mechanical alloying process do not suffice to explain the differences in transformation rates observed here. A parameter, which takes into account the influence of the mechanical properties of grinding materials, is considered.
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  • 4
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    Journal of materials synthesis and processing 8 (2000), S. 271-277 
    ISSN: 1573-4870
    Keywords: Comminution ; kinetics ; mechanical alloying ; phase transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract It has been shown that structural evolution occurring in powder mixtures subjected to mechanical treatment by milling follow well-defined conversion trends as a function of milling time. Sigmoidal curves were observed in the case of the mechanical alloying of transition metal mixtures, whereas a simpler kinetic course with a progressively decreasing transformation rate was found to characterize the disordering process of intermetallic equilibrium compounds by mechanical milling. Under the stipulation that collisions are the dominant energy transfer events, a kinetic model is developed to relate the observed macrokinetic features to the discrete powder fractions, which transform at each impact. Because of its intrinsic qualities, the milling process was regarded as discrete processing. A statistical approach was followed to work out a set of differential equations, solutions of which provide a sound description of the transformation kinetics in terms of conventional rate expressions. The model allows one to reproduce the different kinetic behaviors by means of a single, unifying mathematical formalism. Furthermore, quantifying the structural evolution rate by suitable kinetic constants permits the exploration of the reactive behavior of a system treated under different milling regimes or to compare, on an absolute basis, different systems processed under similar conditions.
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  • 5
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    Oxidation of metals 53 (2000), S. 351-360 
    ISSN: 1573-4889
    Keywords: Co-base superalloy ; high-temperature oxidation ; kinetics ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of the Co-base superalloy DZ40M was studied in air at900–1100°C for times of up to 2000 hr. The results indicated thatthis alloy can grow a protective oxide scale at 900 and 1000°C duringisothermal oxidation, but not at 1100°C because of serious cracking andspalling of the oxide scales. Moreover, an internal-precipitate zone formedin the subsurface region of the alloy at all temperatures and times. Theprecipitates were rich in Cr in the vicinity of the alloy–scaleinterface and rich in Al deep in the alloy. The internal-precipitatemorphology changed from a granular to needlelike shape with increasingoxidation temperature.
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  • 6
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    Powder metallurgy and metal ceramics 39 (2000), S. 540-544 
    ISSN: 1573-9066
    Keywords: compaction ; facing ; cumulative charge ; powder ; composite ; heterogeneous structure ; particle ; kinetics ; surface ; die ; model ; xeroradiogram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An experimental and numerical (finite element method) study is carried out for the effect of forming scheme on property distribution for cumulative charge facings made from composite heterogeneous powder material. An experimental procedure is developed for studying powder particle flow kinetics. It is shown that use of composite punches and partition of the moulded material into a number of sub-divisions with their successive compaction achieves a more uniform density distribution for an article. It is demonstrated how the direction of the force of friction on the die walls during compaction affects the compaction of articles with faces that are not perpendicular to the direction of the pressing. The results obtained make it possible to select the optimum compaction regime taking account of production features connected with powder material composition as well as service characteristics.
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  • 7
    ISSN: 1573-515X
    Keywords: Bouteloua eriopoda ; Chihuahuan Desert ; desertification ; hydrology ; Larrea tridentata ; nitrogen ; nutrient budgets ; phosphorus ; runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Losses of dissolved nutrients (N, P, K, Ca, Mg, Na,Cl, and SO4) in runoff were measured on grasslandand shrubland plots in the Chihuahuan desert ofsouthern New Mexico. Runoff began at a lowerthreshold of rainfall in shrublands than ingrasslands, and the runoff coefficient averaged 18.6%in shrubland plots over a 7-year period. In contrast,grassland plots lost 5.0 to 6.3% of incidentprecipitation in runoff during a 5.5-year period. Nutrient losses from shrubland plots were greater thanfrom grassland plots, with nitrogen losses averaging0.33 kg ha−1 yr−1 vs0.15 kg ha−1 yr−1, respectively, during a 3-year period. Thegreater nutrient losses in shrublands were due tohigher runoff, rather than higher nutrientconcentrations in runoff. In spite of these nutrientlosses in runoff, all plots showed net accumulationsof most elements due to inputs from atmosphericdeposition. Therefore, loss of soil nutrients byhillslope runoff cannot, by itself, account for thedepletion of soil fertility associated withdesertification in the Chihuahuan desert.
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  • 8
    ISSN: 1573-515X
    Keywords: gaseous ; kinetics ; mercury ; methods ; speciation ; waters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Mercury evasion from water is commonly modeled using measurements of dissolved gaseous mercury (DGM). We developed a method using a recently available automated field-ready mercury vapor analyzer to rapidly measure the concentrations of DGM in surface waters. We summarize here results of laboratory tests of the method, field intercomparisons with a manual method, and selected data from recent sampling campaigns in Florida and Michigan. The method uses the 1.5 lpm flow of a Tekran® Model 2537A mercury analyzer to purge and analyze discrete water samples, generating near real time (5-min) data on DGM in samples and blanks. Application of the Tekran allowed for detailed analysis of DGM removal kinetics and short-term diel studies characterizing the influence of sunlight and precipitation on DGM production in surface waters. Gas removal kinetics for dozens of samples indicates a first-order rate constant, and supports a 20-min. purge time for surface water samples from Florida (40-min for Michigan samples). Blanks are measured during a second such purge. Our results indicate that DGMs determined by both automated and manual methods are generally comparable, and that DGM in Florida samples is unstable during storage (loss rate constant ∼0.1--0.2 h-1), probably due to oxidation. This suggests that rapid in-field analysis is preferred to storage with delayed analysis. Our data indicate that DGM at the Florida site is influenced by inputs of reactive Hg in rainwater, and by production of surface DGM during photoreduction of oxidized Hg in the water column.
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  • 9
    ISSN: 1573-515X
    Keywords: C:N ratio ; dissolved organic carbon ; dissolved organic nitrogen ; nitrogen ; stream chemistry ; watershed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Relatively high deposition ofnitrogen (N) in the northeastern United States hascaused concern because sites could become N saturated.In the past, mass-balance studies have been used tomonitor the N status of sites and to investigate theimpact of increased N deposition. Typically, theseefforts have focused on dissolved inorganic forms ofN (DIN = NH4-N + NO3-N) and have largelyignored dissolved organic nitrogen (DON) due todifficulties in its analysis. Recent advances in themeasurement of total dissolved nitrogen (TDN) havefacilitated measurement of DON as the residual of TDN− DIN. We calculated DON and DIN budgets using data onprecipitation and streamwater chemistry collected from9 forested watersheds at 4 sites in New England. TDNin precipitation was composed primarily of DIN. Netretention of TDN ranged from 62 to 89% (4.7 to 10 kghaminus 1 yrminus 1) of annual inputs. DON made up themajority of TDN in stream exports, suggesting thatinclusion of DON is critical to assessing N dynamicseven in areas with large anthropogenic inputs of DIN.Despite the dominance of DON in streamwater,precipitation inputs of DON were approximately equalto outputs. DON concentrations in streamwater did notappear significantly influenced by seasonal biologicalcontrols, but did increase with discharge on somewatersheds. Streamwater NO3-N was the onlyfraction of N that exhibited a seasonal pattern, withconcentrations increasing during the winter months andpeaking during snowmelt runoff. Concentrations ofNO3-N varied considerably among watersheds andare related to DOC:DON ratios in streamwater. AnnualDIN exports were negatively correlated withstreamwater DOC:DON ratios, indicating that theseratios might be a useful index of N status of uplandforests.
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  • 10
    ISSN: 1573-515X
    Keywords: acid deposition ; atmospheric deposition ; nitrate ; nitrification ; nitrogen ; soil carbon ; soil chemistry ; stream water acidification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Cumulative effects of atmospheric N deposition mayincrease N export from watersheds and contribute tothe acidification of surface waters, but naturalfactors (such as forest productivity and soildrainage) that affect forest N cycling can alsocontrol watershed N export. To identify factors thatare related to stream-water export of N, elevationalgradients in atmospheric deposition and naturalprocesses were evaluated in a steep, first-orderwatershed in the Catskill Mountains of New York, from1991 to 1994. Atmospheric deposition of SO 4 2− , andprobably N, increased with increasing elevation withinthis watershed. Stream-water concentrations ofSO 4 2− increased with increasing elevationthroughout the year, whereas stream-waterconcentrations of NO 3 − decreased withincreasing elevation during the winter and springsnowmelt period, and showed no relation with elevationduring the growing season or the fall. Annual exportof N in stream water for the overall watershed equaled12% to 17% of the total atmospheric input on thebasis of two methods of estimation. This percentagedecreased with increasing elevation, from about 25%in the lowest subwatershed to 7% in the highestsubwatershed; a probable result of an upslope increasein the thickness of the surface organic horizon,attributable to an elevational gradient in temperaturethat slows decomposition rates at upper elevations. Balsam fir stands, more prevalent at upper elevationsthan lower elevations, may also affect the gradient ofsubwatershed N export by altering nitrification ratesin the soil. Variations in climate and vegetationmust be considered to determine how future trends inatmospheric deposition will effect watershed export ofnitrogen.
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  • 11
    ISSN: 1573-515X
    Keywords: carbon ; landscape geochemical flows ; model ; nitrogen ; phosphorus ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The importance of landscape geochemical flows wasinvestigated using a dynamic model simulating carbon,nitrogen and phosphorus cycling in riverine wetlands,which has been described in a previous paper. Thehydro-geomorphic unit (HGMU) concept was incorporatedin the model by defining a separate, completeunit-model for each unit (HGMU) within the wetland.These unit-models were connected by defining the flowsof nitrogen and phosphorus between them. These flows,also called landscape geochemical flows, usuallyconsist of flows of water containing N and P. The model was applied to a site at Kismeldon Meadows,in south-western England. This site consists of twounits, a slope and a floodplain, separated by a ditch,which catches most of the run off and shallowgroundwater flows from the slope. Only an estimated1% of the N and P that leaves the slope unit in thewater outflow reaches the floodplain unit; the rest iscaught in the system of ditches, which prevent thegeochemical flows taking their natural course. Toexamine the influence of this system of ditches, themodel was run for the same site, but without theditches. This is comparable to a situation of arestored site, where run off and shallow groundwaterflows containing nutrients, can freely get from theslope to the floodplain. The computer simulation experiment reconnecting theslope and floodplain showed that this (1) increasedthe nutrient input into the floodplain, causing ahigher biomass production, and (2) increased thewetness of the floodplain, causing slowerdecomposition, which together (3) led to a faster soilorganic matter accumulation in the floodplain.Nutrient inflows became relatively more importantcompared to atmospheric deposition, especially forphosphorus. By connecting the slope and the floodplainmore nitrogen and less phosphorus flowed into theriver.
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  • 12
    ISSN: 1573-515X
    Keywords: chloride ; internal eutrophication ; nitrogen ; peat soil ; phosphorus ; phytometer ; sulphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Inputs of surface waters high in chloride and sulphateincreased the availability of nutrients in fenpeatlands. This `internal eutrophication' wasdemonstrated with test plants (`phytometers') andthrough water and soil analysis. Three experiments arepresented in which the level of chloride and/orsulphate was increased to 3 mmolc l−1. Inexperiment 1 chloride levels were increased from 0.5to 3 mmolc l−1 as CaCl2 or NaCl. Inexperiment 2 and 3 similar increased levels forchloride and sulphate (3 mmolc l−1; as NaCland Na2SO4) were used. The following resultswere found: (i) No differences in soil total-N and total-P werefound before and after the treatments in any of thethree experiments. (ii) Experiment 1 showed a significant increase inBio-Available P (BAP) in pots planted with Anthoxanthum odoratum as well as in bare pots for theNaCl and CaCl2 treatments. The plants in thesetreatments had taken up much more P. (iii) Experiment 2 showed an increase in soil BAPafter treatment with chloride and sulphate in potsplanted with Anthoxanthum odoratum. The chloridetreatment had no effect on plant biomass, whereas thesulphate treatment resulted in a reduction in rootbiomass and root N and P content. The shoots showedan increase in P content in the sulphate and chloridetreatments, while N content remained the same. (iv) In experiment 3, treatments with chloride andsulphate led to significantly increased biomass and Puptake of Anthoxanthum odoratum. Again, noeffects on N uptake were found. These experiments provide evidence for distinctlyincreased availability of phosphate in peat soils whenthese come into contact with water with evenmoderately increased sulphate or chloride levels.Surface water originating from the Rhine river, whichis enriched in chloride and sulphate, is oftensupplied to fen reserves in The Netherlands, tocompensate for water losses due to agriculturaldrainage in the region. The results of this study showthat phosphate availability to the vegetation may risedrastically, with detrimental effects on the speciesdensity and the occurrence of rare species in thevegetation. Hence, supply of this water should beavoided.
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  • 13
    ISSN: 1573-2746
    Keywords: 8-hydroxyquinaldine ; electropolymerization ; adsorption ; glassy carbon ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The kinetics and thermodynamics of the electropolymerization of the chelating agent 8-hydroxyquinaldine on GCE's (Glassy Carbon Electrodes') surface from aqueous phosphate buffers are reported. Thermodynamic functions related to the adsorption of the monomer on the GCE's surfaces were determinated. No contribution from GCE surface's functional group to the electropolymerization reactions was reported. The effects of monomer concentration, pH, and temperature on the electrochemical growth of poly 8-hydroxyquinaldine were investigated. The results suggest that the propagation of the electropolymerization process takes place via a free radical chain reactions. Furthermore, the results indicate that the electrochemical growth of the polymeric films is dictated by pre-polymerization adsorption on the electrode surface.
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  • 14
    ISSN: 1572-8900
    Keywords: Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 15
    ISSN: 1572-8986
    Keywords: Arc ; gliding arc ; gas temperature ; electron temperature ; ion composition ; ion bombardment ; liquid electrode ; dye oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The plasma–solution interaction processes for gliding and “point” arcs between the aqueous solution surface and the metal electrode in the gas phase are studied. The plasma, liquid, and surface zones are taken into consideration. The electric field strength is measured, and the gas and electron temperatures and ion composition are estimated for the plasma zone. The cathode fall, water vaporization rate, and active species current yield due to the radiation chemistry mechanism are determined for the surface zone. The efficiency of oxidation of iodine ions and organic dyes by different types of discharge in the liquid zone are investigated. The difference in action of the various discharge types may be connected with various influences of the plasma and surface zone on the oxidation processes.
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  • 16
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    Journal of materials synthesis and processing 7 (1999), S. 311-319 
    ISSN: 1573-4870
    Keywords: Iron ; carbon ; nitrogen ; microstructure ; characterization ; HIP-drip
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A new processing technique makes nitrogen alloying possible by adding nitrogen under elevated nitrogen pressure to prealloyed Fe-C ingots during continuous casting, producing a whole new class of precipitation-free, iron–carbon–nitrogen alloys. When both carbon and nitrogen bulk concentration levels exceeded 0.5 wt%, a duplex fcc-/(bcc-bct-) Fe microstructure resulted that is iron carbide- and nitride-free. With increasing carbon and nitrogen concentrations, there was an increase in the retained fcc-Fe phase. In cooling rate studies, increasing carbon and nitrogen concentrations shifted the knee of the fcc-Fe-to-bcc-Fe phase time–temperature–transformation (T–T–T) curve to longer times. Hardness, compression strength, and wear resistance increased with increasing carbon and nitrogen concentrations and were superior to iron–carbon alloys without the nitrogen addition.
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  • 17
    ISSN: 1573-868X
    Keywords: Osaka Bay ; sediment ; carbon ; nitrogen ; organic matter ; stable isotope ratio ; terrestrial organic matter ; TOC ; POC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract Carbon and nitrogen stable isotope ratios (δ13C and δ15N) of surface sediments were measured within Osaka Bay, in the Seto Inland Sea in Japan, in order to better understand the sedimentation processes operating on both terrestrial and marine organic matter in the Bay. The δ13C and δ15N of surface sediments in the estuary of the Yodo River were less than −23‰ and 5‰ respectively, but increased in the area up to about 10 km from the river mouth. At greater distances they became constant (giving δ13C of about −20‰ and δ15N about 6‰). It can be concluded that large amounts of terrestrial organic matter exist near the mouth of the Yodo River. Stable isotope ratios in the estuary of the Yodo River within 10 km of the river mouth were useful indicators allowing study of the movement of terrestrial organic matter. Deposition rates for total organic carbon (TOC) and total nitrogen (TN) over the whole of the Bay were estimated to be 63,100 ton C/year and 7,590 ton N/year, respectively. The deposition rate of terrestrial organic carbon was estimated to be 13,200 (range 2,000–21,500) ton C/year for the whole of Osaka Bay, and terrestrial organic carbon was estimated to be about 21% (range 3–34) of the TOC deposition rate. The ratio of the deposition rate of terrestrial organic carbon to the rate inflow of riverine TOC and particulate organic carbon (POC) were estimated to be 19% (range 3–31) and 76% (range 12–100), respectively.
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  • 18
    ISSN: 1573-515X
    Keywords: Baltic Sea ; cyanobacteria ; estuaries ; grazing ; iron ; lakes ; molybdenum ; nitrogen ; nitrogen fixation ; nitrogen limitation ; Zooplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Explaining the nearly ubiquitous absence of nitrogen fixation by planktonic organisms in strongly nitrogen-limited estuaries presents a major challenge to aquatic ecologists. In freshwater lakes of moderate productivity, nitrogen limitation is seldom maintained for long since heterocystic, nitrogen-fixing cyanobacteria bloom, fix nitrogen, and alleviate the nitrogen limitation. In marked contrast to lakes, this behavior occurs in only a few estuaries worldwide. Primary production is limited by nitrogen in most temperate estuaries, yet no measurable planktonic nitrogen fixation occurs. In this paper, we present the hypothesis that the absence of planktonic nitrogen fixers from most estuaries is due to an interaction of bottom-up and top-down controls. The availability of Mo, a trace metal required for nitrogen fixation, is lower in estuaries than in freshwater lakes. This is not an absolute physiological constraint against the occurrence of nitrogen-fixing organisms, but the lower Mo availability may slow the growth rate of these organisms. The slower growth rate makes nitrogen-fixing cyanobacteria in estuaries more sensitive to mortality from grazing by Zooplankton and benthic organisms. We use a simple, mechanistically based simulation model to explore this hypothesis. The model correctly predicts the timing of the formation of heterocystic, cyanobacterial blooms in freshwater lakes and the magnitude of the rate of nitrogen fixation. The model also correctly predicts that high Zooplankton biomasses in freshwaters can partially suppress blooms of nitrogen-fixing cyanobacteria, even in strongly nitrogen-limited lakes. Further, the model indicates that a relatively small and environmentally realistic decrease in Mo availability, such as that which may occur in seawater compared to freshwaters due to sulfate inhibition of Mo assimilation, can suppress blooms of heterocystic cyanobacteria and prevent planktonic nitrogen fixation. For example, the model predicts that at a Zooplankton biomass of 0.2 mg l−1, cyanobacteria will bloom and fix nitrogen in lakes but not in estuaries of full-strength seawater salinity because of the lower Mo availability. Thus, the model provides strong support for our hypothesis that bottom-up and top-down controls may interact to cause the absence of planktonic nitrogen fixation in most estuaries. The model also provides a basis for further exploration of this hypothesis in individual estuarine systems and correctly predicts that planktonic nitrogen fixation can occur in low salinity estuaries, such as the Baltic Sea, where Mo availability is greater than in higher salinity estuaries.
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  • 19
    ISSN: 1573-515X
    Keywords: N15 ; nitrogen ; nutrient cycling ; plants ; stable isotopes ; soil ; temperate forest ; tropical forest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Several lines of evidence suggest that nitrogen in most tropical forests is relatively more available than N in most temperate forests, and even that it may function as an excess nutrient in many tropical forests. If this is correct, tropical forests should have more open N cycles than temperate forests, with both inputs and outputs of N large relative to N cycling within systems. Consequent differences in both the magnitude and the pathways of N loss imply that tropical forests should in general be more 15N enriched than are most temperate forests. In order to test this hypothesis, we compared the nitrogen stable isotopic composition of tree leaves and soils from a variety of tropical and temperate forests. Foliar δ15N values from tropical forests averaged 6.5‰ higher than from temperate forests. Within the tropics, ecosystems with relatively low N availability (montane forests, forests on sandy soils) were significantly more depleted in 15N than other tropical forests. The average δ15N values for tropical forest soils, either for surface or for depth samples, were almost 8‰ higher than temperate forest soils. These results provide another line of evidence that N is relatively abundant in many tropical forest ecosystems.
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  • 20
    ISSN: 1573-515X
    Keywords: estuaries ; lakes ; marine ; nitrogen ; phosphorus ; rivers ; streams ; temperate ; tropics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Published data and analyses from temperate and tropical aquatic systems are used to summarize knowledge about the potential impact of land-use alteration on the nitrogen biogeochemistry of tropical aquatic ecosystems, identify important patterns and recommend key needs for research. The tropical N-cycle is traced from pre-disturbance conditions through the phases of disturbance, highlighting major differences between tropical and temperate systems that might influence development strategies in the tropics. Analyses suggest that tropical freshwaters are more frequently N-limited than temperate zones, while tropical marine systems may show more frequent P limitation. These analyses indicate that disturbances to pristine tropical lands will lead to greatly increased primary production in freshwaters and large changes in tropical freshwater communities. Increased freshwater nutrient flux will also lead to an expansion of the high production, N- and light-limited zones around river deltas, a switch from P- to N-limitation in calcareous marine systems, with large changes in the community composition of fragile mangrove and reef systems. Key information gaps are highlighted, including data on mechanisms of nutrient transport and atmospheric deposition in the tropics, nutrient and material retention capacities of tropical impoundments, and N/P coupling and stoichiometric impacts of nutrient supplies on tropical aquatic communities. The current base of biogeochemical data suggests that alterations in the N-cycle will have greater impacts on tropical aquatic ecosystems than those already observed in the temperate zone.
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  • 21
    ISSN: 1573-515X
    Keywords: Baltic Sea ; cyanobacteria ; estuaries ; grazing ; iron ; lakes ; molybdenum ; nitrogen ; nitrogen fixation ; nitrogen limitation ; zooplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Explaining the nearly ubiquitous absence of nitrogen fixation by planktonic organisms in strongly nitrogen-limited estuaries presents a major challenge to aquatic ecologists. In freshwater lakes of moderate productivity, nitrogen limitation is seldom maintained for long since heterocystic, nitrogen-fixing cyanobacteria bloom, fix nitrogen, and alleviate the nitrogen limitation. In marked contrast to lakes, this behavior occurs in only a few estuaries worldwide. Primary production is limited by nitrogen in most temperate estuaries, yet no measurable planktonic nitrogen fixation occurs. In this paper, we present the hypothesis that the absence of planktonic nitrogen fixers from most estuaries is due to an interaction of bottom-up and top-down controls. The availability of Mo, a trace metal required for nitrogen fixation, is lower in estuaries than in freshwater lakes. This is not an absolute physiological constraint against the occurrence of nitrogen-fixing organisms, but the lower Mo availability may slow the growth rate of these organisms. The slower growth rate makes nitrogen-fixing cyanobacteria in estuaries more sensitive to mortality from grazing by zooplankton and benthic organisms. We use a simple, mechanistically based simulation model to explore this hypothesis. The model correctly predicts the timing of the formation of heterocystic, cyanobacterial blooms in freshwater lakes and the magnitude of the rate of nitrogen fixation. The model also correctly predicts that high zooplankton biomasses in freshwaters can partially suppress blooms of nitrogen-fixing cyanobacteria, even in strongly nitrogen-limited lakes. Further, the model indicates that a relatively small and environmentally realistic decrease in Mo availability, such as that which may occur in seawater compared to freshwaters due to sulfate inhibition of Mo assimilation, can suppress blooms of heterocystic cyanobacteria and prevent planktonic nitrogen fixation. For example, the model predicts that at a zooplankton biomass of 0.2 mg l−1, cyanobacteria will bloom and fix nitrogen in lakes but not in estuaries of full-strength seawater salinity because of the lower Mo availability. Thus, the model provides strong support for our hypothesis that bottom-up and top-down controls may interact to cause the absence of planktonic nitrogen fixation in most estuaries. The model also provides a basis for further exploration of this hypothesis in individual estuarine systems and correctly predicts that planktonic nitrogen fixation can occur in low salinity estuaries, such as the Baltic Sea, where Mo availability is greater than in higher salinity estuaries.
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  • 22
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    Biogeochemistry 44 (1999), S. 93-118 
    ISSN: 1573-515X
    Keywords: Everglades National Park ; mangrove soils ; organic matter ; nitrogen ; phosphorus ; sedimentation ; simulation model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The distribution and accumulation of organic matter, nitrogen (N) and phosphorus (P) in mangrove soils at four sites along the Shark River estuary of south Florida were investigated with empirical measures and a process-based model. The mangrove nutrient model (NUMAN) was developed from the SEMIDEC marsh organic matter model and parameterized with data from mangrove wetlands. The soil characteristics in the four mangrove sites varied greatly in both concentrations and profiles of soil carbon, N and P. Organic matter decreased from 82% in the upstream locations to 30% in the marine sites. Comparisons of simulated and observed results demonstrated that landscape gradients of soil characteristics along the estuary can be adequately modeled by accounting for plant production, litter decomposition and export, and allochthonous input of mineral sediments. Model sensitivity analyses suggest that root production has a more significant effect on soil composition than litter fall. Model simulations showed that the greatest change in organic matter, N, and P occurred from the soil surface to 5 cm depth. The rapid decomposition of labile organic matter was responsible for this decrease in organic matter. Simulated N mineralization rates decreased quickly with depth, which corresponded with the decrease of labile organic matter. The increase in organic matter content and decrease in soil bulk density from mangrove sites at downstream locations compared to those at upstream locations was controlled mainly by variation in allochthonous inputs of mineral matter at the mouth of the estuary, along with gradients in mangrove root production. Research on allochthonouns sediment input and in situ root production of mangroves is limited compared to their significance to understanding nutrient biogeochemistry of these wetlands. More accurate simulations of temporal patterns of nutrient characteristics with depth will depend on including the effects of disturbance such as hurricanes on sediment redistribution and biomass production.
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  • 23
    ISSN: 1573-515X
    Keywords: Chaohu Lake ; chemical fertilizer ; cycling ; denitrification ; multipond system ; nitrogen ; nutrient budget ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract During a two-year field study, an annual nutrient budget and cycles were developed for a small agricultural watershed. The study emphasized the integrated unit of the watershed in understanding the biogeochemistry. It was found that the total nutrient input was 39.1× 104 kg nitrogen and 3.91×104 kg phosphorus in the year 1995, of which the greatest input of nutrients to the watershed was chemical fertilizer application, reaching 34.7×104 kg (676 kg/ha) nitrogen and 3.88×104 kg (76 kg/ha) phosphorus. The total nutrient output from the watershed was 13.55×104 kg nitrogen and 0.40×104 kg phosphorus, while the largest output of nitrogen was denitrification, accounting for 44.1% of N output; the largest output of phosphorus was sale of crops, accounting for 99.4% of P output. The results show that the nutrient input is larger than output, demonstrating that there is nutrient surplus within the watershed, a surplus which may become a potential source of nonpoint pollution to area waters. The research showed that both denitrification and volatilization of nitrogen are key ways of nitrogen loss from the watershed. This suggests that careful management of fertilizer application will be important for the sustainable development of agriculture. The research demonstrated that a multipond system within the watershed had high retention rate for both water and nutrients, benefiting the water, nutrient and sediment recycling in the terrestrial ecosystem and helping to reduce agricultural nonpoint pollution at its source. Therefore, this unique watershed system should be recommended due to its great potential relevance for sustainable agricultural development.
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  • 24
    ISSN: 1573-515X
    Keywords: Chihuahuan desert ; desert ; desertification ; grassland ; nitrogen ; nutrient budgets ; phosphorus ; runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rainfall simulation experiments were performed in areas of semiarid grassland (Bouteloua eriopoda) and arid shrubland (Larrea tridentata) in the Chihuahuan desert of New Mexico. The objective was to compare the runoff of nitrogen (N) and phosphorus (P) from these habitats to assess whether losses of soil nutrients are associated with the invasion of grasslands by shrubs. Runoff losses from grass- and shrub-dominated plots were similar, and much less than from bare plots located in the shrubland. Weighted average concentrations of total dissolved N compounds in runoff were greatest in the grassland (1.72 mg/1) and lowest in bare plots in the shrubland (0.55 mg/1). More than half of the N transported in runoff was carried in dissolved organic compounds. In grassland and shrub plots, the total N loss was highly correlated to the total volume of discharge. We estimate that the total annual loss of N in runoff is 0.25 kg/ha/yr in grasslands and 0.43 kg/ha/yr in shrublands — consistent with the depletion of soil N during desertification of these habitats. Losses of P from both habitats were very small.
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  • 25
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    Biogeochemistry 44 (1999), S. 93-118 
    ISSN: 1573-515X
    Keywords: Everglades National Park ; mangrove soils ; organic matter ; nitrogen ; phosphorus ; sedimentation ; simulation model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The distribution and accumulation of organic matter, nitrogen (N) and phosphorus (P) in mangrove soils at four sites along the Shark River estuary of south Florida were investigated with empirical measures and a process-based model. The mangrove nutrient model (NUMAN) was developed from the SEMIDEC marsh organic matter model and parameterized with data from mangrove wetlands. The soil characteristics in the four mangrove sites varied greatly in both concentrations and profiles of soil carbon, N and P. Organic matter decreased from 82% in the upstream locations to 30% in the marine sites. Comparisons of simulated and observed results demonstrated that landscape gradients of soil characteristics along the estuary can be adequately modeled by accounting for plant production, litter decomposition and export, and allochthonous input of mineral sediments. Model sensitivity analyses suggest that root production has a more significant effect on soil composition than litter fall. Model simulations showed that the greatest change in organic matter, N, and P occurred from the soil surface to 5 cm depth. The rapid decomposition of labile organic matter was responsible for this decrease in organic matter. Simulated N mineralization rates decreased quickly with depth, which corresponded with the decrease of labile organic matter. The increase in organic matter content and decrease in soil bulk density from mangrove sites at downstream locations compared to those at upstream locations was controlled mainly by variation in allochthonous inputs of mineral matter at the mouth of the estuary, along with gradients in mangrove root production. Research on allochthonouns sediment input and in situ root production of mangroves is limited compared to their significance to understanding nutrient biogeochemistry of these wetlands. More accurate simulations of temporal patterns of nutrient characteristics with depth will depend on including the effects of disturbance such as hurricanes on sediment redistribution and biomass production.
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  • 26
    ISSN: 1573-515X
    Keywords: Chaohu Lake ; chemical fertilizer ; cycling ; denitrification ; multipond system ; nitrogen ; nutrient budget ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract During a two-year field study, an annual nutrient budget and cycles were developed for a small agricultural watershed. The study emphasized the integrated unit of the watershed in understanding the biogeochemistry. It was found that the total nutrient input was 39.1 × 104 kg nitrogen and 3.91 × 104 kg phosphorus in the year 1995, of which the greatest input of nutrients to the watershed was chemical fertilizer application, reaching 34.7 × 104 kg (676 kg/ha) nitrogen and 3.88 × 104 kg (76 kg/ha) phosphorus. The total nutrient output from the watershed was 13.55 × 104 kg nitrogen and 0.40 × 104 kg phosphorus, while the largest output of nitrogen was denitrification, accounting for 44.1% of N output; the largest output of phosphorus was sale of crops, accounting for 99.4% of P output. The results show that the nutrient input is larger than output, demonstrating that there is nutrient surplus within the watershed, a surplus which may become a potential source of nonpoint pollution to area waters. The research showed that both denitrification and volatilization of nitrogen are key ways of nitrogen loss from the watershed. This suggests that careful management of fertilizer application will be important for the sustainable development of agriculture. The research demonstrated that a multipond system within the watershed had high retention rate for both water and nutrients, benefiting the water, nutrient and sediment recycling in the terrestrial ecosystem and helping to reduce agricultural nonpoint pollution at its source. Therefore, this unique watershed system should be recommended due to its great potential relevance for sustainable agricultural development.
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  • 27
    ISSN: 1573-515X
    Keywords: atmospheric deposition ; moss ; bog ; nitrogen ; phosphorus ; water table
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen additions as NH4NO3 corresponding to 0 (N0), 1 (N1), 3 (N3) and 10 (N10) g N m−2 yr−1 were made toSphagnum magellanicurn cores at two-week intervalsin situ at four sites across Europe, i.e. Lakkasuo (Finland). Männikjärve (Estonia), Moidach More (UK) and Côte de Braveix (France). The same treatments were applied in a glasshouse experiment in Neuchâtel (Switzerland) in which the water table depth was artificially maintained at 7, 17 and 37 cm below the moss surface. In the field, N assimilation in excess of values in wet deposition occurred in the absence of growth, but varied widely between sites, being absent in Lakkasuo (moss N∶P ratio 68) and greatest in Moidach More (N∶P 21). In the glasshouse, growth was reduced by lowering the water table without any apparent effect on N assimilation. Total N content of the moss in field sites increased as the mean depth of water table increased indicating growth limitation leading to increased N concentrations which could reduce the capacity for N retention. Greater contents of NH4 + in the underlying peat at 30 cm depth, both in response to NH4NO3 addition and in the unamended cores confirmed poor retention of inorganic N by the moss at Lakkasuo. Nitrate contents in the profiles at Lakkasuo, Moidach More, and Côte de Braveix were extremely low, even in the N10 treatment, but in Männikjärve, where the mean depth of water table was greatest and retention absent, appreciable amounts of NO3 − were detected in all cores. It is concluded that peatland drainage would reduce the capture of inorganic N in atmospheric deposition bySphagnum mosses.
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  • 28
    ISSN: 1573-515X
    Keywords: N15 ; nitrogen ; nutrient cycling ; plants ; stable isotopes ; soil ; temperate forest ; tropical forest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Several lines of evidence suggest that nitrogen in most tropical forests is relatively more available than N in most temperate forests, and even that it may function as an excess nutrient in many tropical forests. If this is correct, tropical forests should have more open N cycles than temperate forests, with both inputs and outputs of N large relative to N cycling within systems. Consequent differences in both the magnitude and the pathways of N loss imply that tropical forests should in general be more15N enriched than are most temperate forests. In order to test this hypothesis, we compared the nitrogen stable isotopic composition of tree leaves and soils from a variety of tropical and temperate forests. Foliar δ15N values from tropical forests averaged 6.5‰ higher than from temperate forests. Within the tropics, ecosystems with relatively low N availability (montane forests, forests on sandy soils) were significantly more depleted in15N than other tropical forests. The average δ15N values for tropical forest soils, either for surface or for depth samples, were almost 8‰ higher than temperate forest soils. These results provide another line of evidence that N is relatively abundant in many tropical forest ecosystems.
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  • 29
    ISSN: 1573-515X
    Keywords: estuaries ; lakes ; marine ; nitrogen ; phosphorus ; rivers ; streams ; temperate ; tropics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Published data and analyses from temperate and tropical aquatic systems are used to summarize knowledge about the potential impact of land-use alteration on the nitrogen biogeochemistry of tropical aquatic ecosystems, identify important patterns and recommend key needs for research. The tropical N-cycle is traced from pre-disturbance conditions through the phases of disturbance, highlighting major differences between tropical and temperate systems that might influence development strategies in the tropics. Analyses suggest that tropical freshwaters are more frequently N-limited than temperate zones, while tropical marine systems may show more frequent P limitation. These analyses indicate that disturbances to pristine tropical lands will lead to greatly increased primary production in freshwaters and large changes in tropical freshwater communities. Increased freshwater nutrient flux will also lead to an expansion of the high production, N- and light-limited zones around river deltas, a switch from P- to N-limitation in calcareous marine systems, with large changes in the community composition of fragile mangrove and reef systems. Key information gaps are highlighted, including data on mechanisms of nutrient transport and atmospheric deposition in the tropics, nutrient and material retention capacities of tropical impoundments, and N/P coupling and stoichiometric impacts of nutrient supplies on tropical aquatic communities. The current base of biogeochemical data suggests that alterations in the N-cycle will have greater impacts on tropical aquatic ecosystems than those already observed in the temperate zone.
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  • 30
    ISSN: 1573-515X
    Keywords: acetate ; carbon dioxide ; hydrogen ; methanogenesis ; iron ; organic carbon ; nitrogen ; redox balance ; rice paddy soil ; sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The potentials for sequential reduction of inorganic electron acceptors and production of methane have been examined in sixteen rice soils obtained from China, the Philippines, and Italy. Methane, CO2, Fe(II), NO 3 - , SO 4 2 , pH, Eh, H2 and acetate were monitored during anaerobic incubation at 30 °C for 120 days. Based on the accumulation patterns of CO2 and CH4, the reduction process was divided into three distinct phases: (1) an initial reduction phase during which most of the inorganic electron acceptors were depleted and CO2 production was at its maximum, (2) a methanogenic phase during which CH4 production was initiated and reached its highest rate, and (3) a steady state phase with constant production rates of CH4 and CO2. The reduction phases lasted for 19 to 75 days with maximum CO2 production of 2.3 to 10.9 μmol d-1 g-1 dry soil. Methane production started after 2 to 87 days and became constant after about 38--68 days (one soil 〉120 days). The maximum CH4 production rates ranged between 0.01 and 3.08 μmol d-1 g-1. During steady state the constant CH4 and CO2 production rates varied from 0.07 to 0.30 μmol d-1 g-1 and 0.02 and 0.28 μmol d-1 g-1, respectively. Within the 120 d of anaerobic incubation only 6--17% of the total soil organic carbon was released into the gas phase. The gaseous carbon released consisted of 61--100% CO2, 〈0.1--35% CH4, and 〈5% nonmethane hydrocarbons. Associated with the reduction of available Fe(III) most of the CO2 was produced during the reduction phase. The electron transfer was balanced between total CO2 produced and both CH4 formed and Fe(III), sulfate and nitrate reduced. Maximum CH4 production rate (r = 0.891) and total CH4 produced (r = 0.775) correlated best with the ratio of soil nitrogen to electron acceptors. Total nitrogen content was a better indicator for “available” organic substrates than the total organic carbon content. The redox potential was not a good predictor of potential CH4 production. These observations indicate that the availability of degradable organic substrates mainly controls the CH4 production in the absence of inorganic electron acceptors.
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  • 31
    ISSN: 1573-515X
    Keywords: acetate ; carbon dioxide ; hydrogen ; methanogenesis ; iron ; organic carbon ; nitrogen ; redox balance ; rice paddy soil ; sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The potentials for sequential reduction of inorganic electron acceptors and production of methane have been examined in sixteen rice soils obtained from China, the Philippines, and Italy. Methane, CO2, Fe(II), NO 3 − , SO 4 2− , pH, Eh, H2 and acetate were monitored during anaerobic incubation at 30 °C for 120 days. Based on the accumulation patterns of CO2 and CH4, the reduction process was divided into three distinct phases: (1) an initial reduction phase during which most of the inorganic electron acceptors were depleted and CO2 production was at its maximum, (2) a methanogenic phase during which CH4 production was initiated and reached its highest rate, and (3) a steady state phase with constant production rates of CH4. and CO2. The reduction phases lasted for 19 to 75 days with maximum CO2 production of 2.3 to 10.9μmol d−1 g−1 dry soil. Methane production started after 2 to 87 days and became constant after about 38–68 days (one soil 〉120 days). The maximum CH4 production rates ranged between 0.01 and 3.08μmol d−1 g−1. During steady state the constant CH4 and CO2 production rates varied from 0.07 to 0.30μmol d−1 g−1 and 0.02 and 0.28μmol d−1 g−1, respectively. Within the 120 d of anaerobic incubation only 6–17% of the total soil organic carbon was released into the gas phase. The gaseous carbon released consisted of 61–100% CO2, 〈0.1–35% CH4, and 〈5% nonmethane hydrocarbons. Associated with the reduction of available Fe(III) most of the CO2 was produced during the reduction phase. The electron transfer was balanced between total CO2 produced and both CH4 formed and Fe(III), sulfate and nitrate reduced. Maximum CH4 production rate (r=0.891) and total CH4 produced (r =0.775) correlated best with the ratio of soil nitrogen to electron acceptors. Total nitrogen content was a better indicator for “available” organic substrates than the total organic carbon content. The redox potential was not a good predictor of potential CH4 production. These observations indicate that the availability of degradable organic substrates mainly controls the CH4 production in the absence of inorganic electron acceptors.
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  • 32
    ISSN: 1573-0662
    Keywords: atmosphere ; kinetics ; nitrate radical ; monoterpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, α-phellandrene, d-limonene, terpinolene and γ-terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, α-phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and γ-terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and α-phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[−(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[−(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and γ-terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.
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  • 33
    ISSN: 1573-0662
    Keywords: δ3-carene ; chlorine atoms ; isoprene ; kinetics ; methacrolein and methyl vinyl ketone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.
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  • 34
    ISSN: 1573-515X
    Keywords: atmospheric deposition ; moss ; bog ; nitrogen ; phosphorus ; water table
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen additions as NH4NO3 corresponding to 0 (N0), 1 (N1), 3 (N3) and 10 (N10) g N m-2 yr-1 were made to Sphagnum magellanicum cores at two-week intervals in situ at four sites across Europe, i.e. Lakkasuo (Finland), Männikjärve (Estonia), Moidach More (UK) and Côte de Braveix (France). The same treatments were applied in a glasshouse experiment in Neuchâtel (Switzerland) in which the water table depth was artificially maintained at 7, 17 and 37 cm below the moss surface. In the field, N assimilation in excess of values in wet deposition occurred in the absence of growth, but varied widely between sites, being absent in Lakkasuo (moss N:P ratio 68) and greatest in Moidach More (N:P 21). In the glasshouse, growth was reduced by lowering the water table without any apparent effect on N assimilation. Total N content of the moss in field sites increased as the mean depth of water table increased indicating growth limitation leading to increased N concentrations which could reduce the capacity for N retention. Greater contents of NH4+ in the underlying peat at 30 cm depth, both in response to NH4NO3 addition and in the unamended cores confirmed poor retention of inorganic N by the moss at Lakkasuo. Nitrate contents in the profiles at Lakkasuo, Moidach More, and Côte de Braveix were extremely low, even in the N10 treatment, but in Männikjärve, where the mean depth of water table was greatest and retention absent, appreciable amounts of NO3- were detected in all cores. It is concluded that peatland drainage would reduce the capture of inorganic N in atmospheric deposition by Sphagnum mosses.
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  • 35
    ISSN: 1573-515X
    Keywords: Chihuahuan desert ; desert ; desertification ; grassland ; nitrogen ; nutrient budgets ; phosphorus ; runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rainfall simulation experiments were performed in areas of semiarid grassland (Bouteloua eriopoda) and arid shrubland (Larrea tridentata) in the Chihuahuan desert of New Mexico. The objective was to compare the runoff of nitrogen (N) and phosphorus (P) from these habitats to assess whether losses of soil nutrients are associated with the invasion of grasslands by shrubs. Runoff losses from grass- and shrub-dominated plots were similar, and much less than from bare plots located in the shrubland. Weighted average concentrations of total dissolved N compounds in runoff were greatest in the grassland (1.72 mg/l) and lowest in bare plots in the shrubland (0.55 mg/l). More than half of the N transported in runoff was carried in dissolved organic compounds. In grassland and shrub plots, the total N loss was highly correlated to the total volume of discharge. We estimate that the total annual loss of N in runoff is 0.25 kg/ha/yr in grasslands and 0.43 kg/ha/yr in shrublands – consistent with the depletion of soil N during desertification of these habitats. Losses of P from both habitats were very small.
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  • 36
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    Tribology letters 7 (1999), S. 67-71 
    ISSN: 1573-2711
    Keywords: alkanethiol ; self‐assembled monolayers ; quartz crystal microbalance ; viscoelasticity ; kinetics ; ellipsometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Quartz crystal microbalance techniques and in situ spectroscopic ellipsometry are used to probe the structure‐dependent intrinsic viscoelastic properties of self‐assembled CH3(CH2)8SH alkanethiol monolayers adsorbed from the gas phase onto Au(111)‐textured substrates. Physisorbed molecules, mixed chemisorbed‐fluid/solid phases and solid‐phase domain boundaries make sequentially dominant contributions to the measured energy dissipation in the growing monolayer. Deviations from Langmuir adsorption kinetics reveal a precursor‐mediated adsorption channel. These studies reveal the impact of structural heterogeneity in tribological studies of monolayer lubricants.
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  • 37
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    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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  • 38
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    Biology and fertility of soils 26 (1998), S. 169-172 
    ISSN: 1432-0789
    Keywords: Key words Urea ; Coated fertilizers ; Ammonium ; nitrogen ; Nitrate nitrogen ; Nitrogen uptake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Understanding the fate of different forms of nitrogen (N) fertilizers applied to soils is an important step in enhancing N use efficiency and minimizing N losses. The growth and N uptake of two citrus rootstocks, Swingle citrumelo (SC), and Cleopatra mandarin (CM), seedlings were evaluated in a pot experiment using a Candler fine sand (hyperthermic, uncoated, Typic Quartzipsamments) without N application or with 400 mg N kg–1 applied as urea or controlled-release fertilizers (CRF; either as Meister, Osmocote, or Poly-S). Meister and Osmocote are polyolefin resin-coated urea with longevity of N release for 270 days (at 25°C). Poly-S is a polymer and sulfur-coated urea with release duration considerably shorter than that of either Meister or Osmocote. The concentrations of 2 M KCl extractable nitrate nitrogen (NO3 –-N) and ammonium nitrogen (NH4 +-N) in the soil sampled 180 days and 300 days after planting were greater in the soil with SC than with CM rootstock seedlings. In most cases, the extractable NH4 + and NO3 – concentrations were greater for the Osmocote treatment compared to the other N sources. For the SC rootstock seedlings, dry weight was greater with Meister or Poly-S compared with either Osmocote or urea. At the end of the experiment, ranking of the various N sources, with respect to total N uptake by the seedlings, was: Meister = Osmocote 〉 Poly-S 〉 Urea 〉 no N for CM rootstock, and Meister = Poly-S = Osmocote 〉 Urea 〉 no N for SC rootstock. The study demonstrated that for a given rate of N application the total N uptake by seedlings was greater for the CRF compared to urea treatment. This suggests that various N losses were lower from the CRF source as compared to those from soluble fertilizers.
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  • 39
    ISSN: 1572-8986
    Keywords: RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Time-resolved mass spectrometry was used for analysis of the plasma reactions in radio frequency (RF) SiCl 4 and SiCl 4 −O 2 discharges as functions of starting partial pressure and electrical power. Molecular concentrations of the reactants and products from SiCl 4 alone and with O 2 were obtained from the mass spectra and used for plotting the kinetic curves. The SiCl 4 and O 2 consumption rates were calculated from the kinetic curves and compared with results of theoretical simulation of the reaction. Direct electron impact decomposition was found to be the main pathway for pure SiCl 4 conversion. On the contrary, the consumption of SiCl 4 in the SiCl 4 +O 2 mixtures was largely chemical. The experimental macrokinetics are in agreement with a model in which oxidation is caused by the atomic oxygen.
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  • 40
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    Journal of materials synthesis and processing 6 (1998), S. 305-309 
    ISSN: 1573-4870
    Keywords: Fractals ; solid state reaction ; kinetics ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In the present research we theoretically studied the kinetics of nucleation-limited solid state reactions as influenced by the fractal properties of solid reagent. We consider the model of equal-sized primary particles assembled in fractal cluster. The geometry of such an object is assumed to be described solely by its fractal dimension D and by upper (R max) and lower (R min) cutoffs of fractality further identified with the overall size of the object and the size of the primary particle correspondingly. Depending on the ratio between R max, R min and the radius of the critical nucleus R nucl the following cases are considered: (1) R max ∼ R nucl. In this case the reaction kinetics is described by the equation: α = 1 − B{ln(k′ τ + 1)}D/(D−3), where B, k′ are constants. Numerical solution of this equation gives rise to n-order reaction kinetics with n & 1. (2) R min ≪ R nucl ≪ R max. In this case under certain conditions there can exist non-trivial critical density ρcrit ≠ 0, 1 that favors the formation of the critical nuclei of the new phase. The asymptotic kinetic equation for large times corresponds to n-order reaction with n = (D + 3)/(D + 1). (3) R min ≪ R nucl ∼ R max′. In this case the reaction follows the first-order kinetics with D-dependent rate constant.
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  • 41
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    Journal of materials synthesis and processing 6 (1998), S. 161-167 
    ISSN: 1573-4870
    Keywords: Alumina ; surface ; kinetics ; diffusion ; SALK
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics of shape evolution of a completely faceted crystal/internal void by surface diffusion was modeled. Arrays of micron-sized cavities were generated in sapphire substrates with known surface orientations using microlithography and ion beam etching and converted to internal intragranular pores of nonequilibrium shape by diffusion bonding of the etched substrate to an identical-orientation unetched sapphire substrate. Pore shape evolution rates during high-temperature anneals were monitored and found to be highly sensitive to the orientation of the substrate surface. The observed evolution rates were compared with the predictions of the kinetic model using diffusivity values for alumina that span the range from the highest to the lowest diffusion constants reported in the literature. The comparison suggests that surface-attachment-limited kinetics (SALK) play a major role in surface mass transport on stable low-index planes of alumina.
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  • 42
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    Biogeochemistry 43 (1998), S. 63-78 
    ISSN: 1573-515X
    Keywords: carbon ; mass balance ; nitrogen ; nitrogen fixation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Ecosystems with high rates of nitrogen fixation often have high loss rates through leaching or possibly denitrification. However, there is no formal theoretical context to examine why this should be the case nor of how nitrogen accumulates in such open systems. Here, we propose a simple model coupling nitrogen inputs and losses to carbon inputs and losses. The nitrogen balance of this model system depends on plant (nitrogen fixer) growth rate, its carrying capacity, N fixed/C fixed, residence time of nitrogen and carbon in biomass, litter decay rate, litter N/C, and fractional loss rate of mineralized nitrogen. The model predicts the requirements for equilibrium in a nitrogen-fixing system, and the conditions on nitrogen fixation and losses in order for the system to accumulate nitrogen and carbon. In particular, the accumulation of nitrogen and carbon in a nitrogen-fixing system depend on an interaction between residence time in vegetation and litter decay rate in soil. To reflect a possible increased uptake of soil nitrogen and decreased respiratory cost of symbiotic nitrogen fixers, the model was then modified so that fixation rate decreased and growth rate increased as nitrogen capital accumulated. These modifications had only small effects on carbon and nitrogen accumulation. This suggests that switching from uptake of atmospheric nitrogen to mineral soil nitrogen as nitrogen capital accumulates simply results in a trade-off between energetic limitations and soil nitrogen limitations to carbon and nitrogen accumulation. Experimental tests of the model are suggested.
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  • 43
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    Biogeochemistry 42 (1998), S. 169-187 
    ISSN: 1573-515X
    Keywords: aridisols ; desertification ; erosion ; geostatistics ; Larrea tridentata ; nitrogen ; phosphorus ; Prosopis glandulosa ; soil heterogeneity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Geostatistical analyses show that the distribution of soil N, P and K is strongly associated with the presence of shrubs in desert habitats. Shrubs concentrate the biogeochemical cycle of these elements in ‘islands of fertility’ that are localized beneath their canopies, while adjacent barren, intershrub spaces are comparatively devoid of biotic activity. Both physical and biological processes are involved in the formation of shrub islands. Losses of semiarid grassland in favor of invading shrubs initiate these changes in the distribution of soil nutrients, which may promote the further invasion and persistence of shrubs and cause potential feedbacks between desertification and the Earth's climate system.
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  • 44
    ISSN: 1573-0662
    Keywords: peroxy radicals ; kinetics ; conjugateddienes ; biogenic VOC ; degradation mechanisms ; tropospheric ozone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The laser flash photolysis/UV absorption spectrometry technique has been used to investigate the kinetics of the peroxy radical permutation reactions (i.e. self and cross reactions) arising from the OH-initiated oxidation of isoprene (2-methyl-1,3-butadiene), and of the simpler, but related conjugated dienes, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene. The results of the two simpler systems are analysed to provide values of the rate coefficients for the 6 peroxy radical permutation reactions of the three types of isomeric peroxy radical produced in each system (T = 298 K, P = 760 Torr). The rate coefficients are all significantly larger than values estimated previously by extrapolation of structure-reactivity relationships based on the kinetics of a limited dataset of simpler radicals containing similar structural features. The results are discussed in terms of trends in self and cross reaction reactivity of primary, secondary and tertiary peroxy radicals containing combinations of allyl, β-hydroxy and δ-hydroxy functionalities. Since the peroxy radicals formed in these systems are structurally very similar to those formed in the isoprene system, the kinetic parameters derived from the results of the simpler systems are used to assist the assignment of kinetic parameters to the 21 permutation reactions of the six types of isomeric peroxy radical generated in the isoprene system. Kinetic models describing the OH-initiated degradation of all three conjugated dienes to first generation products in the absence of NOx are recommended, which are also consistent with available end product studies. The model for isoprene is considered to be a further improvement on that suggested previously for its OH-initiated oxidation in the absence of NOx. The mechanism is further extended to include chemistry applicable to ‘NOx-present’ conditions, and calculated product yields are compared with those reported in the literature.
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  • 45
    ISSN: 1573-0662
    Keywords: hydroxyl radical ; nitrate radical ; ozone ; pinonaldehyde ; caronaldehyde ; sabinaketone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10−12 cm3 molecule−1 s−1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10−14 cm3 molecule−1 s−1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of 〈2 × 10−20 cm3 molecule−1 s−1 for pinonaldehyde and caronaldehyde, and 〈5 × 10−20 cm3 molecule−1 s−1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.
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  • 46
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    Interface science 6 (1998), S. 113-131 
    ISSN: 1573-2746
    Keywords: discontinuous reactions ; discontinuous precipitation ; discontinuous coarsening ; discontinuous dissolution ; grain boundary ; migration ; diffusion ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Discontinuous reactions are a special class of solid state moving boundary reactions characterized by a discontinuous change in orientation and composition across the migrating reaction front that provides a short circuit path of solute transport. Grain boundary migration in discontinuous reactions is both of technological as well as fundamental interest. In this paper, the initiation/growth mechanism, product morphology, driving force, reaction kinetics, and effect of external parameters on the major discontinuous reactions, namely, discontinuous precipitation, coarsening, dissolution, and diffusion induced grain boundary migration have been discussed. In addition, a number of interesting features about boundary migration in discontinuous reactions has been analyzed. Finally, the scope and necessity of continued research attention in this area have been highlighted.
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  • 47
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    Interface science 6 (1998), S. 267-278 
    ISSN: 1573-2746
    Keywords: grain boundaries ; kinetics ; thermal activation ; activation entropy ; activation enthalpy ; compensation effect ; interfaces
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Extensive experimental evidence is provided for the occurrence of the compensation effect, i.e., the linear dependence of the activation energy on the logarithm of the preexponential factor in interface kinetics, primarily grain boundary migration. It is proposed to attribute the compensation effect to a first order phase transition from the ground state to the activated state during thermal activation. The model is in line with the thermodynamic principles of phase transitions as well as the fundamentals of irreversible thermodynamics. It is capable of accounting for important phenomenological relations of interface kinetics.
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  • 48
    ISSN: 1432-0789
    Keywords: Key words Microbial biomass C ; Water-soluble organic carbon ; Light fraction organic carbon ; Fertilizer ; nitrogen ; 13C nuclear magnetic resonance ; Infrared spectrophotometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Soil samples taken from four experimental sites that had been cropped to continuous corn for 3–11 years in Ontario and Quebec were analyzed to evaluate changes in quantity and quality of labile soil organic carbon under different nitrogen (N) fertility and tillage treatments. Addition of fertilizer N above soil test recommendations tended to decrease amounts of water-soluble organic carbon (WSOC) and microbial biomass carbon (MBC). The quality of the WSOC was characterized by 13C nuclear magnetic resonance and infrared spectrophotometry and the results indicated that carbohydrates, long-chain aliphatics and proteins were the major components of all extracts. Similar types of C were present in all of the soils, but an influence of management was evident. The quantity of soil MBC was positively related to the quantities of WSOC, carbohydrate C, and organic C, and negatively related to quantities of long-chain aliphatic C in the soil. The quantity of WSOC was positively related to the quantities of protein C, carbohydrate C, and negatively related to the quantity of carboxylic C. The quantity of soil MBC was not only related to quantities of soil WSOC but also to the quality of soil WSOC.
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  • 49
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    Biology and fertility of soils 26 (1997), S. 31-34 
    ISSN: 1432-0789
    Keywords: Key words Microbial biomass ; Air-drying ; Extractable ; nitrogen ; Extractable phosphorus ; Tropical soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The microbial contribution to extractable N and P after the air-drying of eight Indian dry tropical Ultisols was quantified. Air-drying of the soils decreased microbial biomass C by 25–53% but increased extractable N and P by 14–34% and 24–121%, respectively. This increase in the extractable N and P was accounted for, to some extent, by microbial biomass killed due to air-drying. Microbial biomass contributes 17–36% and 19–82% to the extractable N and P, respectively, possibly due to air-drying of the soils. I conclude that due to contamination of microbial biomass with the available nutrients in air-dried soils, measurements of extractable nutrients should be made on field-moist soils.
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  • 50
    ISSN: 1573-4889
    Keywords: oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 51
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; iron ; iron-nitride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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  • 52
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    Oxidation of metals 48 (1997), S. 171-184 
    ISSN: 1573-4889
    Keywords: TiAl, corrosion ; high-temperature ; kinetics ; nitrogen dependence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxide scale formation on γ-TiAl at 800 and 900°C was studied using high temperature X-ray diffraction as anin situ-method. The experiments were performed in air and in He with 20 vol.% O2. The formation of alumina in the form of α-Al2O3 and of TiO2 in the form of rutile was observed in both atmospheres and the formation of TiN was detected in air. Depending on the atmosphere the diffraction peaks of two different additional phases were detected, which do not exist in any data base nor in the Ti-Al-O phase diagram. One of them, the Z-phase, appears in He with 20 vol.% O2 and the other, the X-phase, in air. The Zphase was also found at room temperature after oxidation at 900°C in air. The growth of both phases, X and Z, starts immediately with the oxidation process and follows the parabolic rate law.
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  • 53
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 54
    ISSN: 1573-4889
    Keywords: binary alloys ; oxidation ; transient state ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
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  • 55
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    Colloid & polymer science 275 (1997), S. 303-306 
    ISSN: 1435-1536
    Keywords: Key words Vesicle ; self-assembly ; hydrotrope ; stopped-flow ; kinetics
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  The kinetics of vesicle formation from a hydrotrope (sodium xylenesulfonate) solution of a surfactant (Laureth 4) is studied by the use of a stopped-flow apparatus combined with a dynamic light scattering device to determine vesicle size in the system. The hydrotrope system studied presents a system with a high surfactant solubilization combined with vesicle formation simply by dilution with water. The kinetic results show a single exponential decay time. The kinetic analysis indicates that the vesicles are formed from a molecular solution which resulted from the shear in the stopped-flow device and grow by monomeric association.
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  • 56
    ISSN: 1435-1536
    Keywords: Key words 3-aminopropyltriethoxy silane ; silica gel ; interaction ; kinetics
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Three silica gel sample systems, modified with 3-amino-propyltriethoxy silane (APTS), were prepared by sequentially sampling the reaction mixture at various time intervals. The concentrations of 3-aminopropylsilyl groups (APS) bound on the silica surface were determined by elemental analysis. For the same sample systems, 29Si NMR intensities of an (–O)4Si species belonging only to the silica gel particles and corrected by a cross-polarization correction factor were also measured. Both the APS-concentrations and the correc-ted 29Si NMR intensities depended upon reaction time, reflecting the rate of the APTS–silica gel reaction. Kinetic analysis of these data was made by use of the Gauss–Newton method, and the overall reaction was found to consist of three reaction processes (an initial fast reaction, a slower second reaction and a much slower third reaction). In particular, the conversion of (–O)3SiOH to (–O)4Si is predominant in the second reaction process and the pore size of a silica gel particle affects the reaction mechanism.
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  • 57
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    Biogeochemistry 36 (1997), S. 189-203 
    ISSN: 1573-515X
    Keywords: ammonia volatilization ; grassland ; nitrogen ; ungulate ; Yellowstone National Park
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured ammonia volatilization at three topographic positions(hilltop, mid-slope, slope-bottom) on three grassland landscapes at threetimes during 1995 (April, May, July) on the northern winter range ofYellowstone National Park that supports large herds of native ungulates.Percent ammonia-N lost from all sites during the study ranged 1–24%of urea-N applied. Volatilization among sites was negatively related tosoil cation-exchange capacity (r = –0.85) and rates were highest inJuly. We used the relationship between soil CEC and percent Nvolatilized from urea-amended plots to estimate annual ammonia-Nvolatilization from 5 sites for which annual ungulate urine inputs werepreviously determined (Frank et al. 1994). Estimated mean annualammonia-N volatilized from those sites was 1.4 kg/ha/yr, which wasless than a previously reported regional atmospheric deposition rate (2kg/ha/yr; Swank 1984). Results indicate the need to understand theinteraction between (1) spatially heterogeneous patterns of soilprocesses, and 2) nonuniform patterns of ungulate use of landscapes todetermine rates of ecosystem-level N-gaseous loss. Findings alsosuggest that ammonia-N volatilized from urine patches should not leadto a decline in soil N in this ecosystem.
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  • 58
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    Biogeochemistry 37 (1997), S. 237-252 
    ISSN: 1573-515X
    Keywords: freshwater ; limitation ; marine ; nitrogen ; phosphorus ; ratio ; stoichiometry ; trace elements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen supply is often assumed to limitmarine primary production. A global analysis of totalnitrogen (N) to phosphorus (P) molar ratios shows thattotal N:P is low (〈16:1) in some estuarine andcoastal ecosystems, but up to 100:1 in open oceans.This implies that elements other than N may limitmarine production, except in human impacted, estuarineor coastal ecosystems. This pattern may reconcileconflicting enrichment studies, because N additionfrequently increases phytoplankton growth where totalN:P is expected to be low, but P, Fe, or Si augmentphytoplankton growth in waters where total N:P ishigh. Comparison of total N:P stoichiometry betweenmarine and freshwaters yields a model of the form ofthe aquatic N:P cycle.
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  • 59
    ISSN: 1573-515X
    Keywords: carbon ; nitrogen ; Ohio River ; phosphorus ; Red field ratios ; dissolved organic matter ; rivers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A 12-month study was conducted to measure the concentrations ofdissolved organic matter (DOC, TDN, TDP) in four sites within a119 km long reach of the Ohio River, near Louisville, KY. In thisstudy we test whether specific geomorphological and biologicalfactors influenced variations in dissolved organic matter.Concentrations of DOC in the river averaged ≈1200μmol/L, and varied by nearly two orders of magnitudeseasonally (mean DOC during base flow ≈620 μmol/L).Peak periods for DOC at all sites were during April–May. Thesite nearest a navigation dam (deeper, lower current velocities)had significantly lower concentrations of TDN and greater C:Nratios than upstream sites. The largest tributary entering thisreach (Kentucky River) had no significant effect on levels of DOMin the main river, despite having significantly greaterconcentrations of TDN and lower levels of DOC during most monthsof the year. Concentrations of DOC, TDN, and TDP were notsignificantly different in littoral and pelagic habitats at allsites studied, suggesting little floodplain influence on DOM inthis constricted-channel section of the Ohio River. C:N ratios ofDOM in the Ohio were significantly different among seasons; C:Nexceeded or equaled Redfield ratios in summer and fall (6 to 10),but were below Redfield (1.8 to 3.0) during winter and spring.Regression models suggest that total phytoplankton densities andflow conditions are the two most important factors regulating DOMin this very large river.
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  • 60
    ISSN: 1573-515X
    Keywords: Amazon ; deforestation ; hydrologic pathway ; groundwater ; nitrogen ; rain forest ; slash-and-burn agriculture ; solutes ; tropical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Hydrochemical changes caused by slash-and-burnagricultural practices in a small upland catchment inthe central Amazon were measured. Soluteconcentrations were analyzed in wet deposition,overland flow, shallow throughflow, groundwater andbank seepage in a forested plot (about 5 ha) and anadjacent plot (about 2 ha) which had been deforestedin July 1989 and planted to manioc, and in streamwater in partially deforested and forested catchments. Measurements were made from November 1988 to June1990. The effects of slash-and-burn agriculturalpractices observed in the experimental plot includedincreased overland flow, erosion, and large losses ofsolutes from the rooted zone. Concentrations ofNO3 -, Na+, K+, SO4 2-,Cl- and Mn in throughflow of the experimentalplot were higher than those of the control plot bymore than a factor of 10. Extensive leaching occurredafter cutting and burning, but solute transfers werediminished along pathway stages of throughflow togroundwater, and particularly within the riparian zoneof the catchment. High concentrations of N and P inoverland flow indicate the importance of usingforested riparian buffers to mitigate solute inputs toreceiving waters in tropical catchments.
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    Biogeochemistry 37 (1997), S. 63-75 
    ISSN: 1573-515X
    Keywords: nutrient limitation ; soil development ; nitrogen ; phosphorus ; chronosequence ; Hawai'i
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Walker & Syers (1976) proposed a conceptual model that describesthe pattern and regulation of soil nutrient pools and availability during long-term soil and ecosystem development. Their model implies that plantproduction generally should be limited by N on young soils and by P on oldsoils; N and P supply should more or less equilibrate onintermediate-aged soils. We tested the application of this model to nutrientlimitation, using a well characterized substrate age sequence in Hawaiianmontane rain forest. Earlier experiments had evaluated nutrient limitationin forests on a young (300 y) and an old (4,100,000 y) substrate on the samedevelopmental sequence; N alone limited tree growth on the youngsubstrate, while P alone did so on the old one. An additional fertilizerexperiment based on replicated treatments with N, P, and all othernutrients combined, applied in individually and in all factorialcombinations, was established in an intermediate-aged site in theLaupahoehoe Forest Reserve, Hawaii. Here, diameter increments of thedominant tree Metrosideros polymorpha increased slightly with Nadditions, and nearly doubled when N and P were added together.Additions of elements other than N and P had no significant effecton growth. These results show that N and P had equilibrated (relativeto plant requirements) in the intermediate aged site. Together withthe earlier experiments, these results suggest that the Walker and Syersmodel provides a useful starting point for explaining the nature anddistribution of nutrient limitation in forest ecosystems.
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  • 62
    ISSN: 1573-515X
    Keywords: aluminium ; forest soils ; lysimeters ; nitrification ; nitrogen ; roots
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The effects of enhanced (NH4 2SO4deposition on soil solution cation and anion concentrations and annualionic fluxes were followed using a standardised experimental protocolin six European coniferous forests with contrasting soil types, pollutioninputs and climate. Native soil cores containing a ceramic suction cupwere installed in the field, roofed and watered every two weeks withlocal throughfall or local throughfall with added(NH4)2SO4 at 75 kgNH4 +-N ha-1 a-1. Livingroot systems were established in half of the lysimeters.Untreated throughfall NH4 +-N deposition at thesites ranged from 3.7 to 29 kg ha-1 a-1Soil leachates were collected at two weekly intervalsover 12 months and analysed for volume, andconcentrations of major anions and cations. Increasesin soil solution NO3 - concentrations inresponse to N additions were observed after 4–9months at three sites, whilst one sandy soil with highC:N ratio failed to nitrify under any of thetreatments. Changes in NO3 - concentrationsin soil solution controlled soil solution cationconcentrations in the five nitrifying soils, withAl3+ being the dominant cation in the more acidsoils with low base saturation. The acidification responses ofthe soils to the (NH4 2SO4additions were primarily related to the ability of thesoils to nitrify the added NH4 +. pH and soiltexture seemed important in controllingNH4 + leaching in response to the treatments,with two less acidic, clay/clay loam sites showingalmost total retention of added NH4 +, whilstnearly 75% of the added N was leached asNH4 + at the acid sandy soils. The presenceof living roots significantly reduced soil solutionNO3 - and associated cation concentrations attwo of the six sites. The very different responses of the sixsoils to increased (NH4)2SO4deposition emphasise that the establishment of N critical loadsfor forest soils need to allow for differences in N storagecapacity and nitrification potential.
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  • 63
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    Biogeochemistry 39 (1997), S. 1-13 
    ISSN: 1573-515X
    Keywords: 226Ra accumulation ; background level ; natural zones ; terrestrial animals ; nitrogen ; rain forest ; slash-and-burn agriculture ; solutes ; tropical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Radium (226Ra) accumulation by terrestrial animalswas studied in the territory of the former USSR. Concentrations of226Ra in different soils, plants and animals aresimilar to the background level. For soils it fluctuates in range0.5–1.5 × 10-12 gg-1 (18.3–55 Bq/kg), for plantsbetween 0.1–1.7 × 10-12 gg-1 (3.7–62.1 Bq/kg), and for animals– 0.02–1.5 ×10-12 g g-1(0.73–55 Bq/kg). There were no significant differences in226Ra concentration between animals of different groups. Themaximal 226Ra concentration is marked for the woodlouse Hemilepistus aphganicus from the Badkhyz reserve in Turkmenistan– 1.49 × 10-12g g-1 of dwt (54.4 Bq/kg), the minimal one– for Colorado beetle Leptinotarsadecemlineata from the vicinity of Moscow – 0.02× 10-12 gg-1 of dwt (0.73 Bq/kg). Concentration ratios for linkssoil – plant, plant – animal andprey – carnivore are usually close to 1. A hypothesison the similarity of 226Raconcentration in different animals is discussed.
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  • 64
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    Journal of elasticity 46 (1997), S. 53-90 
    ISSN: 1573-2681
    Keywords: phase transitions ; kinetics ; traveling waves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The theory of thermoelastic materials undergoing solid-solid phase transformations requires constitutive information that governs the evolution of a phase boundary. This is known as a kinetic relation which relates a driving traction to the speed of propagation of a phase boundary. The kinetic relation is prescribed in the theory from the onset. Here, though, a special kinetic relation is derived from an augmented theory that includes viscous, strain gradient and heat conduction effects. Based on a special class of solutions, namely travelling waves, the kinetic relation is inherited from the augmented theory as the viscosity, strain gradient and heat conductivity are removed by a suitable limit process.
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  • 65
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    Pure and applied geophysics 147 (1996), S. 367-375 
    ISSN: 1420-9136
    Keywords: Induced seismicity ; kinetics ; rock fracture ; rockburst ; earthquake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Powerful seismic events, such as earthquakes and rockbursts, are caused by the accumulation of energy in rocks and loss of rock mass stability. Usually methods of their forecasting are based on the registration of anomalous behavior of geophysical fields. However an efficiency of this approach is low. The present paper proposes a kinetic approach to the description of rock fracture process, which can be used for the forecasting of seismic events and an investigation of structure and energy distributions in rock. 3-D and 1-D kinetic equations describing a process of cluster formation in rock were obtained. The equations are invariant to deformation conditions and to the scale level of events. They showed a good agreement with the results of field observations and laboratory experiments. It was also shown that these equations well describe the processes of earthquake, rockburst and rock sample failure preparation. Catalogues of rockbursts in mines were analyzed with the use of the kinetic equations to find out evidence of induced seismic events. The proposed approach makes it possible to reveal trends in rock behavior and thus predict the rock failure at different scale levels.
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  • 66
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    Plasma chemistry and plasma processing 16 (1996), S. 577-603 
    ISSN: 1572-8986
    Keywords: Cathode erosion ; electrode materials ; argon ; nitrogen ; hydrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Cathode erosion continues to be a problem hindering the widespread application of plasma technology. In this work, cathode erosion was studied on titanium, stainless steel 314, copper-nickel 10% and 30%, and copper 122 for magnetically rotated arcs operating in argon, nitrogen, and argon/hydrogen mixtures at a constant magnetic flux density of 0.1 T Titanium and stainless steel gave very low erosion rates in argon (0.2 and 0.3, μg/C respectively). Cupronickels were shown to be suitable for nitrogen and hydrogen plasmas. The slope of hydrogen solubility versus temperature in the cathode material was found to be important in determining hydrogen plasma erosion characteristics. When the plasma gas has a high solubility in the cathode material, or can react with the cathode, a negative erosion rate may result. When gas solubility in the cathode is low, oxide stability and mode of electron emission may govern the erosion rate. A high gas solubility in the cathode material, as with hydrogen, can result in mechanical erosion due to micro-explosions near the cathode surface.
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  • 67
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    Acta mechanica Sinica 12 (1996), S. 144-157 
    ISSN: 1614-3116
    Keywords: microstructural evolution ; energetics ; kinetics ; dynamic system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract An evolving material structure is in a non-equilibrium state, with free energy expressed by the generalized coordinates. A global approach leads to robust computations for the generalized thermodynamic forces. Those forces drive various kinetic processes, causing dissipation at spots, along curves, surfaces and interfaces, and within volumetric regions. The actual evolution path, and therefore the final equilibrium state, is determined by the energetics and kinetics. A virtual work principle links the free energy landscape and the kinetic processes, and assigns a viscous environment to every point on the landscape. The approach leads to a dynamical system that governs the evolution of generalized coordinates. The microstructural evolution is globally characterized by a basin map in the coordinate space; and by a diversity map and a variety map in the parameter space. The control of basin boundaries raises the issue of energetic and kinetic bifurcations. The variation of basin boundaries under different sets of controlling parameters provides an analytical way to plot the diversity maps of structural evolution.
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  • 68
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    Biogeochemistry 32 (1996), S. 93-113 
    ISSN: 1573-515X
    Keywords: alpine ; biogeochemistry ; nitrogen ; nitrogen saturation ; snowmelt ; soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Experiments were conducted during 1993 at Niwot Ridge in the Colorado Front Range to determine if the insulating effect of winter snow cover allows soil microbial activity to significantly affect nitrogen inputs and outputs in alpine systems. Soil surface temperatures under seasonal snowpacks warmed from −14 °C in January to 0 °C by May 4th. Snowmelt began in mid-May and the sites were snow free by mid June. Heterotrophic microbial activity in snow-covered soils, measured as C02 production, was first identified on March 4, 1993. Net C02 flux increased from 55 mg CO2-C m−2 day−1 in early March to greater than 824 mg CO2-C m-2 day−1 by the middle of May. Carbon dioxide production decreased in late May as soils became saturated during snowmelt. Soil inorganic N concentrations increased before snowmelt, peaking between 101 and 276 mg kg−1 soil in May, and then decreasing as soils became saturated with melt water. Net N mineralization for the period of March 3 to May 4 ranged from 2.23 to 6.63 g N m−2, and were approximately two orders of magnitude greater than snowmelt inputs of 50.4 mg N m−2 for NH4 + and 97.2 mg N m−2 for NO3 −. Both NO3 − and NH4 + concentrations remained at or below detection limits in surface water during snowmelt, indicating the only export of inorganic N from the system was through gaseous losses. Nitrous oxide production under snow was first observed in early April. Production increased as soils warned, peaking at 75 μg N2O-N m−2 day−1 in soils saturated with melt water one week before the sites were snow free. These data suggest that microbial activity in snow-covered soils may play a key role in alpine N cycling before plants become active.
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  • 69
    ISSN: 1573-515X
    Keywords: lacustrine sediment ; organic matter ; sedimentation rates ; recycling ; burial ; carbon ; nitrogen ; silicon ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The areal distribution of organic C contents, δ13C values, total N and P and biogenic Si contents in surficial sediments were used to study the distribution, origin and diagenetic transformations of sedimented biogenic debris in the eutrophic subalpine Lake Bled (Slovenia), which for most of the yearhas an anoxic hypolimnion. The influence of an allochthonous input, restricted to the western basin, was clearly traced by higher organic C and total N and P contents, higher δ13C values, and higher sedimentation rate in comparison to the eastern basin. The low δ13C values of sedimentary organic matter in the major part of the lake, lower than the δ13C values of different types of organic matter, suggest that this sedimentary organic matter is most probably the product of a microbial community and not a residue of primary production. The temporal variation of benthic diffusive fluxes of NH4, Si and PO4, derived from modelling the pore water profiles, was related to sedimentation of phytoplanktonic blooms, while the PO4 fluxes were also dependent on changing redox conditions at the sediment-water interface in the period of the winter-spring overtum. The removal of PO4 in pore waters is probably due to the adsorption of phosphate and precipitation of apatite and vivianite. The budget of C, N and P at the sediment-water interface revealed a high recycling efficiency (〉70%), also confirmed by the rather uniform (or only slightly decreasing) vertical profiles of organic C, total N and P in sediment cores and C/N and C/P ratios. The percentage of biogenic Si recycling is low (〈10%), suggesting its removal in sediments.
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  • 70
    ISSN: 1573-515X
    Keywords: continental shelf ; estuaries ; mass balance ; nitrogen ; North Atlantic ; nutrient budget ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Five large rivers that discharge on the western North Atlantic continental shelf carry about 45% of the nitrogen (N) and 70% of the phosphorus (P) that others estimate to be the total flux of these elements from the entire North Atlantic watershed, including North, Central and South America, Europe, and Northwest Africa. We estimate that 61 · 109 moles y−1 of N and 20 · 109 moles y−1 of P from the large rivers are buried with sediments in their deltas, and that an equal amount of N and P from the large rivers is lost to the shelf through burial of river sediments that are deposited directly on the continental slope. The effective transport of active N and P from land to the shelf through the very large rivers is thus reduced to 292 · 109 moles y−1 of N and 13 · 109 moles y−1 of P. The remaining riverine fluxes from land must pass through estuaries. An analysis of annual total N and total P budgets for various estuaries around the North Atlantic revealed that the net fractional transport of these nutrients through estuaries to the continental shelf is inversely correlated with the log mean residence time of water in the system. This is consistent with numerous observations of nutrient retention and loss in temperate lakes. Denitrification is the major process responsible for removing N in most estuaries, and the fraction of total N input that is denitrified appears to be directly proportional to the log mean water residence time. In general, we estimate that estuarine processes retain and remove 30–65% of the total N and 10–55% of the total P that would otherwise pass into the coastal ocean. The resulting transport through estuaries to the shelf amounts to 172–335 · 109 moles y−1 of N and 11–19 · 109 moles y−1 of P. These values are similar to the effective contribution from the large rivers that discharge directly on the shelf. For the North Atlantic shelf as a whole, N fluxes from major rivers and estuaries exceed atmospheric deposition by a factor of 3.5–4.7, but this varies widely among regions of the shelf. For example, on the U.S. Atlantic shelf and on the northwest European shelf, atmospheric deposition of N may exceed estuarine exports. Denitrification in shelf sediments exceeds the combined N input from land and atmosphere by a factor of 1.4–2.2. This deficit must be met by a flux of N from the deeper ocean. Burial of organic matter fixed on the shelf removes only a small fraction of the total N and P input (2–12% of N from land and atmosphere; 1–17% of P), but it may be a significant loss for P in the North Sea and some other regions. The removal of N and P in fisheries landings is very small. The gross exchange of N and P between the shelf and the open ocean is much larger than inputs from land and, for the North Atlantic shelf as a whole, it may be much larger than the N and P removed through denitrification, burial, and fisheries. Overall, the North Atlantic continental shelf appears to remove some 700–950· 109 moles of N each year from the deep ocean and to transport somewhere between 18 and 30 · 109 moles of P to the open sea. If the N and P associated with riverine sediments deposited on the continental slope are included in the total balance, the net flux of N to the shelf is reduced by 60 · 109 moles y−1 and the P flux to the ocean is increased by 20 · 109 moles y−1. These conclusions are quite tentative, however, because of large uncertainties in our estimates of some important terms in the shelf mass balance.
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    Journal of atmospheric chemistry 24 (1996), S. 23-37 
    ISSN: 1573-0662
    Keywords: hydroxyl radical ; dimethylsulfoxide ; kinetics ; sulfur cycle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10-10 cm3 molecule-1 s-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10-17 cm2, where the large uncertainty results from experimental difficulties associated with the low vapor pressure and ‘stickiness’ of DMSO.
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  • 72
    ISSN: 1573-515X
    Keywords: fertilizer study ; Hawaii ; montane tropical forest ; nitrogen ; phosphorus ; primary succession
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We applied fertilizers in a 23complete factorial design to determine the effects of nutrient amendments on plant growth in Hawaiian montane forests growing on two different volcanic substrates: ‘a‘ā and pāhoehoe lava. Both sites were about 140 years old and their overstories were nearly monospecific stands of Metrosideros polymorpha. Fertilizer applications included N, P, a mixture of essential macro- and micronutrients excepting P and N, and all combinations thereof in each of four blocks. Additions of nutrients other than N or P had no significant effects on measured plant-growth variables. In contrast, additions of either N or P significantly increased tree height growth, diameter increments, biomass growth, and height growth of the understory fern Dicranopteris linearis in both sites. The effect of N was greater than that of P. Greatest growth rates occurred in plots receiving both N and P, and signficant N*P interactions occurred in several cases, suggesting a synergistic effect between these two elements. Plant growth on these young, poorly weathered, basaltic lavas is colimited by N and P availability. Growth in a similar-aged stand growing on a mixture of volcanic ash and cinders is N but not P limited, indicating that the texture of the parent material influences nutrient-availability patterns during early primary succession.
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  • 73
    ISSN: 1573-515X
    Keywords: biogeochemistry ; mangrove ; sediments ; organic carbon ; nitrogen ; carbonate dissolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The biogeochemistry of mangrove sediments was investigated in several mangrove forest communities in Gazi Bay, a coastal lagoon in Kenya, Africa. Carbon dioxide fluxes, sediment median grain sizes, sedimentary organic carbon, nitrogen and phosphorus contents and pore-water characteristics (ammonium, nitrate, sulfate and chloride) could be related to forest type. Mangrove sediments have pH values that range from 3.5 to 8.3 due to the limited buffer capacity of these sediments and intense acidifying processes such as aerobic degradation of organic matter, oxidation of reduced components, ammonium uptake by roots and root respiration. The mangrove sediments are nitrogen-rich compared to mangrove litter, as a result of microbial nitrogen retention, uptake and fixation, and import of nitrogen-rich material. It appears that mangrove sediments in Gazi Bay act as a nutrient and carbon sink rather than as a source for adjacent seagrass and reef ecosystems.
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  • 74
    ISSN: 1573-515X
    Keywords: anthropogenic ; atmospheric deposition ; eutrophication ; fertilizer ; nitrogen ; nitrogen budget ; nitrogen fixation ; N:P ratio ; phosphorus ; pristine ; rivers ; temperate ; tropical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We present estimates of total nitrogen and total phosphorus fluxes in rivers to the North Atlantic Ocean from 14 regions in North America, South America, Europe, and Africa which collectively comprise the drainage basins to the North Atlantic. The Amazon basin dominates the overall phosphorus flux and has the highest phosphorus flux per area. The total nitrogen flux from the Amazon is also large, contributing 3.3 Tg yr−1 out of a total for the entire North Atlantic region of 13.1 Tg yr−1 . On a per area basis, however, the largest nitrogen fluxes are found in the highly disturbed watersheds around the North Sea, in northwestern Europe, and in the northeastern U.S., all of which have riverine nitrogen fluxes greater than 1,000 kg N km−2 yr−1. Non-point sources of nitrogen dominate riverine fluxes to the coast in all regions. River fluxes of total nitrogen from the temperate regions of the North Atlantic basin are correlated with population density, as has been observed previously for fluxes of nitrate in the world's major rivers. However, more striking is a strong linear correlation between river fluxes of total nitrogen and the sum of anthropogenically-derived nitrogen inputs to the temperate regions (fertilizer application, human-induced increases in atmospheric deposition of oxidized forms of nitrogen, fixation by leguminous crops, and the import/export of nitrogen in agricultural products). On average, regional nitrogen fluxes in rivers are only 25% of these anthropogenically derived nitrogen inputs. Denitrification in wetlands and aquatic ecosystems is probably the dominant sink, with storage in forests perhaps also of importance. Storage of nitrogen in groundwater, although of importance in some localities, is a very small sink for nitrogen inputs in all regions. Agricultural sources of nitrogen dominate inputs in many regions, particularly the Mississippi basin and the North Sea drainages. Deposition of oxidized nitrogen, primarily of industrial origin, is the major control over river nitrogen export in some regions such as the northeastern U.S. Using data from relatively pristine areas as an index of change, we estimate that riverine nitrogen fluxes in many of the temperate regions have increased from pre-industrial times by 2 to 20 fold, although some regions such as northern Canada are relatively unchanged. Fluxes from the most disturbed region, the North Sea drainages, have increased by 6 to 20 fold. Fluxes from the Amazon basin are also at least 2 to 5 fold greater than estimated fluxes from undisturbed temperate-zone regions, despite low population density and low inputs of anthropogenic nitrogen to the region. This suggests that natural riverine nitrogen fluxes in the tropics may be significantly greater than in the temperate zone. However, deforestation may be contributing to the tropical fluxes. In either case, projected increases in fertilizer use and atmospheric deposition in the coming decades are likely to cause dramatic increases in nitrogen loading to many tropical river systems.
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  • 75
    ISSN: 1573-515X
    Keywords: methane oxidation ; methane emission ; soil ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Measurements of the net methane exchange over a range of forest, moorland, and agricultural soils in Scotland were made during the period April to June 1994 and 1995. Fluxes of CH4 ranged from oxidation −12.3 to an emission of 6.8 ng m−2 s−1. The balance between CH4 oxidation and emission depended on the physical conditions of the soil, primarily soil moisture. The largest oxidation rates were found in the mineral forest soils, and CH4 emission was observed in several peat soils. The smallest oxidation rate was observed in an agricultural soil. The relationship between CH4 flux and soil moisture observed in peats (FluxCH 4 = 0.023 × %H2O (dry weight) − 7.44, p 〉 0.05) was such that CH4 oxidation was observed at soil moistures less than 325%( ± 80%). CH4 emission was found at soil moistures exceeding this value. A large range of CH4 oxidation rates were observed over a small soil moisture range in the mineral soils. CH4 oxidation in mineral soils was negatively correlated with soil bulk density (FluxCH 4 = −37.35 × bulk density (g cm−3) + 48.83, p 〉 0.05). Increased nitrogen loading of the soil due to N fixation, atmospheric deposition of N, and fertilisation, were consistently associated with decreases in the soil sink for CH4, typically in the range 50 to 80%, on a range of soil types and land uses.
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    Biogeochemistry 35 (1996), S. 261-274 
    ISSN: 1573-515X
    Keywords: budget ; new production ; nitrogen ; nitrogen fixation ; North Atlantic ; Trichodesmium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The role of nitrogen fixation in the nitrogen cycle of the North Atlantic basin was re-evaluated because recent estimates had indicated a far higher rate than previous reports. Examination of the available data on nitrogen fixation rates and abundance ofTrichodesmium, the major nitrogen fixing organism, leads to the conclusion that rates might be as high as 1.09 × 1012 mol N yr−1. Several geochemical arguments are reviewed that each require a large nitrogen source that is consistent with nitrogen fixation, but the current data, although limited, do not support a sufficiently high rate. However, recent measurements of the fixation rates per colony are higher than the historical average, suggesting that improved methodology may require a re-evaluation through further measurements. The paucity of temporally resolved data on both rates and abundance for the major areal extent of the tropical Atlantic, where aeolian inputs of iron may foster high fixation rates, represents another major gap.
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  • 77
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    Biogeochemistry 35 (1996), S. 235-260 
    ISSN: 1573-515X
    Keywords: benthic mineralization ; continental shelf ; denitrification ; global N cycle ; nitrogen ; North Atlantic ; nutrients ; onwelling ; phytoplankton ; sediments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A model of coupled nitrification/denitrification was developed for continental shelf sediments to estimate the spatial distribution of denitrification throughout shelf regions in the North Atlantic basin. Using data from a wide range of continental shelf regions, we found a linear relationship between denitrification and sediment oxygen uptake. This relationship was applied to specific continental shelf regions by combining it with a second regression relating sediment oxygen uptake to primary production in the overlying water. The combined equation was: denitrification (mmol N m−2 d−1)=0.019* phytoplankton production (mmol C m−2 d−1). This relationship suggests that approximately 13% of the N incorporated into phytoplankton in shelf waters is eventually denitrified in the sediments via coupled nitrification/denitrification, assuming a C:N ratio of 6.625:1 for phytoplankton. The model calculated denitrification rates compare favorably with rates reported for several shelf regions in the North Atlantic. The model-predicted average denitrification rate for continental shelf sediments in the North Atlantic Basin is 0.69 mmol N m− 2 d−1. Denitrification rates (per unit area) predicted by the model are highest for the continental shelf region in the western North Atlantic between Cape Hatteras and South Florida and lowest for Hudson Bay, the Baffin Island region, and Greenland. Within latitudinal belts, average denitrification rates were lowest in the high latitudes, intermediate in the tropics and highest in the mid-latitudes. Although denitrification rates per unit area are lowest in the high latitudes, the total N removal by denitrification (53 × 1010 mol N y−1) is similar to that in the mid-latitudes (60 × 1010 mol N y−1) due to the large area of continental shelf in the high latitudes. The Gulf of St. Lawrence/Grand Banks area and the North Sea are responsible for seventy-five percent of the denitrification in the high latitude region. N removal by denitrification in the western North Atlantic (96 × 1010 mol N y−1) is two times greater than in the eastern North Atlantic (47 × 1010 mol N y−1). This is primarily due to differences in the area of continental shelf in the two regions, as the average denitrification rate per unit area is similar in the western and eastern North Atlantic. We calculate that a total of 143 × 1010 mol N y−1 is removed via coupled nitrification/denitrification on the North Atlantic continental shelf. This estimate is expected to underestimate total sediment denitrification because it does not include direct denitrification of nitrate from the overlying water. The rate of coupled nitrification/denitrification calculated is greater than the nitrogen inputs from atmospheric deposition and river sources combined, and suggests that onwelling of nutrient rich slope water is a major source of N for denitrification in shelf regions. For the two regions where N inputs to a shelf region from onwelling have been measured, onwelling appears to be able to balance the denitrification loss.
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  • 78
    ISSN: 1573-515X
    Keywords: nitrogen ; particulate organic matter ; nutrient cycling ; grassland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A set of long term15N studies was initiated during the summers of 1981 and 1982 on the backslope and footslope, respectively, of a catena in the shortgrass steppe of northeastern Colorado. Microplots labeled with15N urea were sampled for15N and total N content in 1981 and 1982 and again in 1992. In November, 1982, 100% of the added N was recovered in the soil-plant system of the finer-textured footslope, compared to 39% in the coarser-textured backslope microplots. Ten years later,15N recovery of the applied N decreased at both topographic positions to 85% in the footslope and 29% in the backslope. Average losses since the time of application were 3.5 g N m−2yr−1 in the backslope and 0.8 g N m−2yr−1 in the footslope. In 1992, soil organic matter was physically fractionated into particulate (POM) and mineral associated (MAON) fractions and 21-day mineralization incubations were conducted to assess the relative amounts of15N that were in the slow, passive and active soil organic matter pools, respectively, of the two soils. Our findings confirm the assumptions that POM represents a large portion of the slow organic compartment and that the MAON represents a large fraction of the passive compartment defined in the Century model. The N located in the MAON had the lowest availability for plant uptake. Isotopic data were consistent with textural effects and with the Century model compartmentalization of soil organic N based on the residence time of the organic N.
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  • 79
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    Interface science 3 (1996), S. 241-267 
    ISSN: 1573-2746
    Keywords: grain boundary segregation ; grain boundary cohesion ; fracture ; kinetics ; equilibrium ; anisotropy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract This feature article summarizes the present art and science of grain boundary segregation from the viewpoint of the authors activities in this field. In the part on equilibrium segregation, fundamental effects on grain boundary segregation are discussed such as the nature of the solute/matrix binary system, presence of additional elements, temperature, grain boundary orientation and type of interface. In addition, the predictive capabilities of grain boundary segregation diagrams are outlined. The present models of segregation kinetics are reviewed and discussed in connection with recent experiments. The last part of the paper is focussed on the most important consequences of grain boundary segregation, i.e., grain boundary cohesion and fracture.
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  • 80
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    Journal of elasticity 44 (1996), S. 271-284 
    ISSN: 1573-2681
    Keywords: martensite ; kinetics ; driving traction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract A purely mechanical, sharp interface model is developed to consider curved interfaces that have been observed between martensite phase variants. The approach is based on a theory of small strains as distinct from small displacement gradients. It admits a realistic characterization of each phase with standard elasticity tensors and allows for inhomogeneous states of strain within each phase including inhomogeneous, finite rotations. The model indicates that any signficant interface curvature must be due to material rotation because interfaces cannot be finitely curved with respect to the material lattice. It is also found that the interface driving traction is not influenced by local lattice rotations unless inertia affects the reaction.
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  • 81
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    Plasma chemistry and plasma processing 15 (1995), S. 279-307 
    ISSN: 1572-8986
    Keywords: Transport coefficients ; transport properties ; viscosity ; thermal conductivity ; electrical conductivity ; diffusion coefficient ; Chapman-Etskog method ; air ; argon ; nitrogen ; oxygen ; plasma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Calculated values of the viscosity, thermal conductivity and electrical conductivity of air and mixtures of air and argon, air and nitrogen, and air and oxygen at high temperatures are presented. In addition, combined ordinary, pressure, and thermal diffusion coefficients are given for the gas mixtures. The calculations, which assione local thermodynamic equilibrium, are performed for atmospheric pressure plasmas in the temperature range from 300 to 30,000 K. The results for air plasmas are compared with those of published theoretical and experimental studies. Significant discrepancies are found with the other theoretical studies; these are attributed to differences in the collision integrals used in calculating the transport coefficients. A number of the collision integrals used here are significantly more accurate than values used previously, resulting in more reliable values of the transport coefficients.
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  • 82
    ISSN: 1573-1421
    Keywords: calcite ; precipitation ; dissolution ; kinetics ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Calcite dissolution rates were measured using a free-drift technique at 25°C, 1 atm total pressure, and various $$P_{CO_2 } $$ in deionized water. The data were corrected for gas phase disequilibrium and fitted to a kinetic expression derived by coupling the mechanistic models of Plummeret al. (1987a) and Chouet al. (1989) to the surface complexation model of Van Cappellenet al. (1993). Corrected dissolution and precipitation rate measurements from previous investigations were combined to our data set and fitted to the same expression. The following reactions provide an adequate description of the calcite dissolution and precipitation mechanism in dilute solutions: for which the overall reaction rate is given by where 〉i are the densities of surface complexes (mol/m2),a i are the activities of dissolved species and,k i are the rate constants corresponding to the above reactions. This rate equation satisfies the principle of microscopic reversibility and applies to both dissolution and precipitation reactions over a wide range of $$P_{CO_2 } $$ , pH and saturation states. The rate constants obtained from fitting the data set to Equation (3) are compatible with values reported by Plummeret al. and Chouet al., as well as yielding a very good estimate of the thermodynamic solubility constant of calcite, K 0 sp .
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  • 83
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    Oxidation of metals 43 (1995), S. 509-526 
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; tantalum ; oxide ; suboxide ; impurities ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics, structural aspects, and phase morphologies were studied for tantalum oxidation in air from 600 to 1000°C for samples of different purity (99.15%, 99.76%, and 99.95% Ta). Regardless of purity, tantalum oxidation in the temperature range of 600–800°C as a rule is governed by a linear rate law. From 900 to 1000°C the initial-stage oxidation is governed by the parabolic rate law, which changes to the linear rate law with time. TGA, XRD, SEM, and AES methods were used. The, effect of purity on tantalum oxidation was shown to be determined by the mechanism of intermediate-oxide formation. They are TaO z (Ta2O) at 600–800°C and TaO at 900–1000°C. The final product of oxidation was β-Ta2O5.
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  • 84
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    Oxidation of metals 43 (1995), S. 543-560 
    ISSN: 1573-4889
    Keywords: stainless steel ; sulfidation ; hydrogen sulfide ; sulfur vapor ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The sulfidizing behavior of Fe−22Cr−4Al−0.15Zr (wt.%) was studied in two atmospheres: S2 vapor over the range 4.4–25.4 Pa and H2−H2S mixtures corresponding to aP S 2 range 0.2–1.297 Pa in the temperature range 973–1373 K. It was found that the constitution of the gaseous phase is of great importance on the corrosion kinetics and the morphology of the corrosion products. Furthermore, a stratification phenomenon during scale growth was observed during the initial sulfidation stage in H2−H2S mixtures containing a sufficiently high H2S partial pressure. This behavior was not observed during tests in puresulfur vapor.
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    Oxidation of metals 44 (1995), S. 63-79 
    ISSN: 1573-4889
    Keywords: scale growth ; oxidation mechanism ; kinetics ; scale adherence ; reactive element effect ; intertacial segregation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Recent studies of the structure and dynamics of solid-solid interfaces have provided some understanding about the role of the scale-metal interface in the growth of reaction product scales on pure metals. The action of interfacial defects (misfit dislocations, misorientation dislocations and disconnections) in the creation and annihilation of the point defects suporting the diffusional growth of scales is considered. Anion point defects (vacancies/interstitials) supporting scale growth by anion diffusion are annihilated/created by the climb of misorientation dislocations or disconnections in the scale at the interface. For scale growth by cation diffusion, cation point defects (vacancies/interstitials) can be annihilated/created by the climb of interfacial misfit or misorientation dislocations in the metal. Because of their necessarily high density, in most cases, the dominant climb of misfit dislocations would be favored. The blocking of interfacial reaction steps can be a means to retard the scaling kinetics and to alter the fundamental scaling mode. For instance, the interfacial segregation of large reactive element ions can pin the interface dislocations, an action which poisons the usual interfacial reaction step. Such considerations are consistent with the well-known phenomena ascribed to the reactive element effect (REE).
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  • 86
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    Colloid & polymer science 273 (1995), S. 524-532 
    ISSN: 1435-1536
    Keywords: Blends ; tetramethyl polycarbonate ; polystyrene ; LCST ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A new method for the detection of phase separation and its kinetics through real-time measurements is presented using the dielectric technique. The kinetics of phase separation were determined for a blend of tetramethyl bisphenol-A polycarbonate TMPC and polystyrene PS at different temperatures. The temperature dependence of the rate constant of phase separation was determined. The activation energy of phase separation process is found to be equal to 46 kcal/mole. In addition, it was possible to determine the variation in the composition of the TMPC-rich phase with time. The results obtained were compared with the literature data and were found to be in good agreement.
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  • 87
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    Biogeochemistry 30 (1995), S. 171-189 
    ISSN: 1573-515X
    Keywords: ammonium ; marsh ; mineralization ; nitrate ; nitrification ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Flooding can be an important control of nitrogen (N) biogeochemistry in wetland ecosystems. In North American prairie marshes, spring flooding is a dominant feature of the physical environment that increases emergent plant production and could influence N cycling. I investigated how spring flooding affects N availability and plant N utilization in whitetop (Scolochloa festucacea) marshes in Manitoba, Canada by comparing experimentally spring-flooded marsh inside an impoundment with adjacent nonflooded marsh. The spring-flooded marsh had net N mineralization rates up to 4 times greater than nonflooded marsh. Total growing season net N mineralization was 124 kg N ha−1 in the spring-flooded marsh compared with 62 kg N ha−1 in the nonflooded marsh. Summer water level drawdown in the spring-flooded marsh decreased net N mineralization rates. Net nitrification rates increased in the nonflooded marsh following a lowering of the water table during mid summer. Growing season net nitrification was 33 kg N ha−1 in the nonflooded marsh but 〈 1 kg N ha−1 in the spring-flooded marsh. Added NO3 −1 induced nitrate reductase (NRA) activity in whitetop grown in pot culture. Field-collected plants showed higher NRA in the nonflooded marsh. Nitrate comprised 40% of total plant N uptake in the nonflooded marsh but 〈1% of total N uptake in the spring-flooded marsh. Higher plant N demand caused by higher whitetop production in the spring-flooded marsh approximately balanced greater net N mineralization. A close association between the presence of spring flooding and net N mineralization and net nitrification rates indicated that modifications to prairie marshes that change the pattern of spring inundation will lead to rapid and significant changes in marsh N cycling patterns.
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  • 88
    ISSN: 1573-515X
    Keywords: budget ; carbon ; mass balance ; Narragansett Bay ; nitrogen ; nutrients ; phosphorus
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Narragansett Bay is a relatively well-mixed, high salinity coastal embayment and estuary complex in southern New England (USA). Much of the shoreline is urban and the watershed is densely developed. We have combined our data on C, N, and P inputs to this system, on C, N, and P accumulation in the sediments, and on denitrification with extensive work by others to develop approximate annual mass balances for these elements. The results show that primary production within the bay is the major source of organic carbon (4 times greater than other sources), that land drainage and upstream sewage and fertilizer are the major sources of N, and that landward flowing bottom water from offshore may be a major source of dissolved inorganic phosphorus. Most of the nutrients entering the bay arrive in dissolved inorganic form, though DON is a significant component of the N carried by the rivers. About 40% of the DIN in the rivers is in the form of ammonia. Sedimentation rates are low in most of Narragansett Bay, and it appears that less than 20% of the total annual input of each of these elements is retained within the system. A very small amount of C, N, and P is removed in fisheries landings, denitrification in the sediments removes perhaps 10–25% of the N input, and most of the carbon fixed in the system is respired within it. Stoichiometric calculations suggest that some 10–20% of the organic matter formed in the bay is exported to offshore and that Narragansett Bay is an autotrophic system. Most of the N and P that enters the bay is, however, exported to offshore waters in dissolved inorganic form. This assessment of the overall biogeochemical behavior of C, N, and P in the bay is consistent with more rigorously constrained mass balances obtained using large living models or mesocosms of the bay at the Marine Ecosystem Research Laboratory (MERL).
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    Colloid & polymer science 273 (1995), S. 1028-1032 
    ISSN: 1435-1536
    Keywords: Hydrolyzed polyacrylamide ; hematite ; adsorption ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The adsorption measurements of hydrolyzed polyacrylamide (HPAM) onto hematite suspension are carried out to study the dynamics of the polymer adsorption onto the suspension particles and to investigate the mode of the polymer adsorption. The polymer is found to show much affinity for the adsorption because of the opposite charges possessed by the polymeric flocculant and the suspension particles. Various adsorption parameters such as adsorption coefficient, the rate constants for the adsorption and desorption, are evaluated with the help of a recently proposed kinetic scheme. It is found that the extent of adsorption and the adsorption rate are adequately affected by increasing the pH of the suspension while, unexpectedly, the adsorption is found to show only a marginal increase on addition of Na2SO4. Both the amount of the adsorbed polymer and the adsorption rate are also found to increase with the degree of hydrolysis of the polyelectrolyte.
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    Biogeochemistry 29 (1995), S. 223-235 
    ISSN: 1573-515X
    Keywords: chronosequence ; montane tropical forest ; nitrogen ; nutrient limitation ; phosphorus ; productivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We tested the hypothesis that P was the nutrient limiting net primary production of a nativeMetrosideros polymorpha forest on a highly weathered montane tropical soil in Hawaii. A factorial experiment used all combinations of three fertilizer treatments: nitrogen (N), phosphorus (P) and a mix of other essential nutrients (OE), consisting primarily of mineral derived cations and excluding N and P. P addition, but not N or OE, increased leaf area index within 12 months, foliar P concentration measured at 18 months, and stem diameter increment within 18 months. Stem growth at 18 months was even greater when trees fertilized with P also received the OE treatment. N and P additions increased leaf litterfall and N and P in combination further increased litterfall. The sequence of responses suggests that increased available P promoted an increase in photosynthetic area which led to increased wood production. P was the essential element most limiting to primary production on old volcanic soil in contrast to the N limitation found on young volcanic soils.
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    Journal of porous materials 2 (1995), S. 9-17 
    ISSN: 1573-4854
    Keywords: adsorption ; isotherm ; characterization ; modeling ; simulation ; pore size ; density functional theory ; argon ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The formalism of (nonlocal) density functional theory provides an attractive way to describe the physical adsorption process at the fluid-solid interface. It provides numerical results of analytic precision in a small fraction of the time required by a simulation technique. In particular, the ability to model adsorption in a pore space of slit-like or cylindrical geometry has led to useful methods for extracting pore size distribution information from experimental adsorption isotherms. However, critical comparisons of experimental isotherms with the isotherms predicted by density functional theory have shown important differences when using the usual prescription for the nonlocal free energy density functional. It is clear that these differences would affect the accuracy of such pore size information. We show in this paper how a small modification to the mean field computation of the intermolecular attractive potential results in excellent agreement with experiment for the systems studied.
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  • 92
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    Aquatic geochemistry 1 (1995), S. 399-426 
    ISSN: 1573-1421
    Keywords: manganese reduction ; manganese oxidation ; organic matter oxidation ; kinetics ; bacteria ; alkalinity ; lake chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The redox processes regulating transport of Mn in the water column of a eutrophic, dimictic lake (Lake Norrviken, Sweden) are interpreted based on a one-dimensional diffusion-reaction model for Mn(II). It is found that rates and rate constants for oxidation and reduction vary greatly with depth and also with time during the season of stratification. Calculated rates show that Mn(II) oxidation and reduction generally occur in narrow depth intervals (25–50 cm). This is in good agreement with measured profiles of particulate Mn (MnO x ). Maximum oxidation rate constants (assuming first order kinetics) at each date are in the first half of the season 〈1 d−1, but then increases to a rather constant value of about 25 d−1. These high rate constants are indicative of microbiological involvement in the Mn(II) oxidation. This is further evidenced by SEM-EDS analysis showing Mn enriched particles morphologically similar toMetallogenium. Reductive dissolution of Mn oxides occurs mainly in the zone just below the zone of maximum oxidation rate. The release of Mn(II) is accompanied by production of alkalinity and ΣCO2. The relation between production rates of Mn(II) and alkalinity indicates that Mn oxides act as terminal electron acceptors in the bacterially mediated oxidation of organic matter. However, the ΔMn2+/ΔΣCO2 ratio is significantly lower than what is expected from this process. It is suggested that the Mn reduction is coupled to fermentation. Close coexistence of Mn reduction and oxidation at high rates, such as found in the water column of this lake, facilitates rapid and continuous regeneration of reducible Mn oxides. This gives rise to a quantitatively important mechanism of organic matter oxidation in the water column.
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  • 93
    ISSN: 1573-0417
    Keywords: Great Basin ; climatic variations ; productivity ; organic matter ; nitrogen ; phosphorus ; hardwater lake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Sediment cores from the shallow and deep basins of Pyramid Lake, Nevada, revealed variations in composition with depth reflecting changes in lake level, river inflow, and lake productivity. Recent sediments from the period of historical record indicate: (1) CaCO3 and organic content of sediment in the shallow basin decrease at lower lake level, (2) CaCO3 content of deep basin sediments increases when lake level decreases rapidly, and (3) the inorganic P content of sediments increases with decreasing lake volume. Variations in sediment composition also indicate several periods for which productivity in Pyramid Lake may have been elevated over the past 1000 years. Our data provide strong evidence for increased productivity during the first half of the 20th Century, although the typical pattern for cultural eutrophication was not observed. The organic content of sediments also suggests periods of increased productivity in the lake prior to the discovery and development of the region by white settlers. Indeed, a broad peak in organic fractions during the 1800's originates as an increase starting around 1600. However, periods of changing organic content of sediments also correspond to periods when inflow to the lake was probably at extremes (e.g. drought or flood) indicating that fluctuations in river inflow may be an important factor affecting sediment composition in Pyramid Lake.
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    Plasma chemistry and plasma processing 14 (1994), S. 451-490 
    ISSN: 1572-8986
    Keywords: Transport coefficients ; transport properties ; viscosity ; thermal conductivity ; electrical conductivity ; diffusion coefficient ; Chapman Enskog method ; argon ; nitrogen ; oxygen ; plasma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Calculated values of the viscosity, thermal conductivity, and electrical conductivity of argon, nitrogen, and oxygen plasmas, and mixtures of argon anti nitrogen and of argon anti oxygen, are presented. In addition, combined ordinary, pressure, and thermal diffusion coefficients are given for the gas mixtures. These three combined diffusion coefficients fully describe di fusion of the two gases, irrespective of their degree of dissociation or ionizati on. The calculations, which assume local thermodynamic equilibrium, are performed! for atmospheric-pressure plasmas in the temperature range /torn 300 to 30,000 K. A number of the collision integrals used in calculating the transport coefficients are significantly more accurate than values used in previous theoretical studies, resulting in more reliable values of the transport coefficients. The results are compared with those of published theoretical and experimental studies.
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  • 95
    ISSN: 1573-4889
    Keywords: niobium ; oxidation ; morphology ; kinetics ; stresses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of niobium at high temperature (900°C) leads to reaction products with “exotic” morphologies. Morphological and kinetics analysis have been undertaken with Nb platelets. A growth mechanism of the oxide at the edges of the platelet is proposed.
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    Oxidation of metals 42 (1994), S. 223-237 
    ISSN: 1573-4889
    Keywords: kinetics ; scale ; oxidation ; zirconium ; purity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of zirconium of different purities were studied over the temperature range of 600–1300°C (α- and β-phases). The structure of the oxidized specimens was examined. TGA, XRD, EPMA, SEM, metallographic analysis, and microhardness measurements were carried out. Impurity elements were found to increase the oxidation rate of technical zirconium. The mechanism of the effect of impurity elements on zirconium oxidation was shown to differ for the α- and β-phases. Activation energies were calculated for the parabolic and linear stages of oxidation.
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    Oxidation of metals 42 (1994), S. 249-263 
    ISSN: 1573-4889
    Keywords: kinetics ; scale ; oxidation ; hafnium ; purity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of hafnium of different purities were studied in the temperature range of 800–1200°C. This paper concerns the structure studies of the oxidized samples. TGA, XRD, SEM methods, and microhardness measurements were used. Hafnium oxidation follows the parabolic rate law, changing with time to the linear one. Oxidation-reaction products are HfO2(moncl) and α-solid solution of oxygen in hafnium. Anomalous oxidation behavior of hafnium having a high impurity content was found in the range 800–950°C. Activation energies for the parabolic and linear oxidation stages were calculated.
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  • 98
    ISSN: 1435-1536
    Keywords: Mn(III)-poly(ethylene glycol) ; acrylonitrile ; block copolymerization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics and mechanism of thermal polymerization of acrylonitrile initiated by Mn(III) pyrophosphate — poly(ethylene glycol) (PEG, molecular weight 6000) redox system in aqueous sulfuric acid medium was studied in the temperature range 30–60°C. The overall rates of polymerization and the disappearance of Mn3+ were determined. The polymerization was initiated by the organic free radical produced from the Mn3+-PEG reaction and the termination was by the metal ions. The rate of polymerization of acrylonitrile was found to be directly proportional to the square of the monomer concentration and first power of PEG concentration, and inversely proportional to the concentration of Mn3+. The rate of manganic ion disappearance was found to be directly proportional to manganic ion concentration and PEG concentration, and independent of the monomer concentration. Based on these observations, a plausible reaction scheme was suggested and suitable kinetic expressions were evaluated.
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    Biogeochemistry 25 (1994), S. 19-39 
    ISSN: 1573-515X
    Keywords: denitrification ; mineralization ; nitrification ; nitrogen ; riparian ; stream ; wetland ; New Jersey ; Pennsylvania ; Pinelands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Denitrification (N2 production) and oxygen consumption rates were measured at ambient field nitrate concentrations during summer in sediments from eight wetlands (mixed hardwood swamps, cedar swamps, heath dominated shrub wetland, herbaceous peatland, and a wetland lacking live vegetation) and two streams. The study sites included wetlands in undisturbed watersheds and in watersheds with considerable agricultural and/or sewage treatment effluent input. Denitrification rates measured in intact cores of water-saturated sediment ranged from ≤ 20 to 260 μmol N m-2 h-1 among the three undisturbed wetlands and were less variable (180 to 260 μmol N M-2 h-1) among the four disturbed wetlands. Denitrification rates increased when nitrate concentrations in the overlying water were increased experimentally (1 up to 770 μM), indicating that nitrate was an important factor controlling denitrification rates. However, rates of nitrate uptake from the overlying water were not a good predictor of denitrification rates because nitrification in the sediments also supplied nitrate for denitrification. Regardless of the dominant vegetation, pH, or degree of disturbance, denitrification rates were best correlated with sediment oxygen consumption rates (r 2 = 0.912) indicating a relationship between denitrification and organic matter mineralization and/or sediment nitrification rates. Rates of denitrification in the wetland sediments were similar to those in adjacent stream sediments. Rates of denitrification in these wetlands were within the range of rates previously reported for water-saturated wetland sediments and flooded soils using whole core15N techniques that quantify coupled nitrification/denitrification, and were higher than rates reported from aerobic (non-saturated) wetland sediments using acetylene block methods.
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    Transport in porous media 16 (1994), S. 237-251 
    ISSN: 1573-1634
    Keywords: phosphate ; soil ; adsorption ; leaching ; kinetics ; computer simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Effects of flow rate and distance travelled on average mobilities of phosphate in a soil are estimated from breakthrough curves of phosphate at the outlets of small columns of soil, following step increases in the concentration at the inlets. Experimental results are compared with results from a computer simulation model of leached columns of soil. Average mobilities of phosphate in columns of soil, following a step increase in the input concentration, decrease with decreasing rate of flow and with increasing distance travelled and appear to be linearly correlated on a logarithmic scale with both flow rate and distance travelled. An empirical equation, describing these relationships, is fitted to data from leaching experiments at flow rates between 30 and 600 cm/day in ≈ 10 cm long columns of soil. Coefficients are obtained by curve fitting breakthrough curves, calculated with a numerical computer simulation model, to experimental breakthrough curves. The fitted equation enables extrapolation to flow rates and travel distances that are more relevant to a field situation.
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