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  • kinetics  (70)
  • phosphorus
  • Springer  (111)
  • Institute of Physics
  • 1995-1999  (111)
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  • 1996  (111)
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  • 1990-1994
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Adsorption 2 (1996), S. 265-277 
    ISSN: 1572-8757
    Keywords: frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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  • 2
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    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Keywords: dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
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  • 3
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    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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  • 4
    ISSN: 1572-882X
    Keywords: accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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  • 5
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    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Keywords: aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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  • 6
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 7
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 8
    ISSN: 1436-5073
    Keywords: kinetics ; rates ; integrating ratemeter ; optimization ; first-order
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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  • 9
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    Nutrient cycling in agroecosystems 46 (1996), S. 81-90 
    ISSN: 1573-0867
    Keywords: elemental sulfur ; granule size ; nitrogen ; phosphorus ; potassium ; S oxidation ; sulfur fertilizers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Experiments were undertaken to determine the effect of granule size and nutrients in granulated compound fertilizers fortified with finely divided elemental sulfur (So) on the rate of So oxidation. In one experiment, So was banded together with or apart from triple superphosphate (TSP) while in two others, So was granulated with nutrient and inert carriers. A fourth experiment examined response to S in an So-fortified TSP from a range of granule sizes. Response and, in some cases, So recovery (using 35S labels) by test crops (maize, wheat, upland rice) was measured. In all experiments, P mixed with So increased plant growth and S recovery above treatments in which P and So were physically separated. There was however, no effect of distance of separation on S recovery. In one experiment, N as urea and N and P as diammonium phosphate (DAP) were also found to enhance response to So although to a lesser degree than P alone. These observations were attributed to a nutritional requirement of So-oxidizing microorganisms for P and N. Granulation of So with carriers also influenced oxidation rate, as inferred from the fertilizer S recovery. For a given So concentration, the effect was inversely proportional to the mean diameter of granules. It is shown that this relationship can be explained if one assumes that So particles in granules collapse into a fixed number of aggregates per granule irrespective of granule size when the soluble nutrient carrier dissolves and diffuses away from the point of application.
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  • 10
    ISSN: 1573-0867
    Keywords: long-term experiments ; phosphorus ; rice ; nutrient balance ; phosphorus uptake ; fertilizer P response ; soil testing ; ion-exchange resin ; phosphorus supplying capacity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Data from long-term experiments at 11 sites in Asia with a wide range of nutrient input treatments and yield levels were used to quantify crop P requirements of rice (Oryza sativa L.) and the P balance in intensive, irrigated rice systems. Uptake of 1.8–4.2 kg P was required to produce one ton of grain yield. Physiological P use efficiency varied between 220 to 900 kg grain kg P-1. Without added P, there was a net loss of 7 to 8 kg P ha-1 per crop; with added P there was a net gain of 4 to 5 kg P ha-1 per crop. Phosphorus adsorption kinetics on mixed-bed ion-exchange resin capsules provided an integrative measure of soil P status, P diffusion, and acid-induced P solubilization. The resin capsule was a sensitive tool to characterize buildup or depletion of soil P as a result of different P balances. Both Olsen-P and the resin capsule were suitable methods to predict P uptake of tropical lowland rice. It is hypothesized that both methods measure a similar soil P pool which is soluble under alkaline, aerobic conditions but transformed into acid-soluble P froms as a result of submergence and reduction. Present recommendations for P fertilizer use on rice of 20–25 kg P ha-1 are adequate to maintain yields of 5–6 t ha-1, but sustaining higher yields of 7–8 t ha-1 will require farm-specific management strategies based on knowledge of the long-term P balance and soil P-supplying capacity.
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  • 11
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    Nutrient cycling in agroecosystems 46 (1996), S. 71-79 
    ISSN: 1573-0867
    Keywords: ammonium poly-phosphate ; diammonium orthophosphate ; fertilizer reaction ; gram ; Indian soils ; phosphorus ; P uptake ; single superphosphate ; triple superphosphate ; yield
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Laboratory studies on the characterization of soil-fertilizer P reaction products were carried out by reacting three-soils occurring in a toposequence in the plateau region of Bihar (India) with saturated solutions of diammonium orthophosphate (DAP), triple superphosphate (TSP) and ammonium polyphosphate (APP) for 1 hour and 24 hours. The reaction products (precipitates) formed in the solutions after 120 days of incubation were isolated and identified through X-ray diffraction technique. Results indicate the formation of Brushite [CaHPO4 · 2H2O, Strengite (FePO4 · 2H2O), Variscite (AIPO4 · 2H2O) and Fe4(P2O7)3 as major soil-fertilizer P reaction products in these soils with ortho-and polyphosphates as source of phosphorus. Pot cultures were used to evaluate the relative efficiency of reaction products (Struvite, Brushite, Variscite and Strengite), orthophosphates (DAP and SSP) and polyphosphate (APP) as sources of P for gram (Cicer arietinum L.) in a typical acid soil. Results indicate significant response of gram to different sources and level of added P. The dry weight and P uptake at 0, 6 and 12 mg P kg-1 soil were 0.406, 0.519 and 0.609 (g pot-1); and 0.289, 0.428 and 0.575 (mg P pot-1), respectively. Among the sources , struvite proved to be superior or equally effective as APP, DAP or SSP as sources of P for gram. Uptake of P also varied significantly with different P sources and levels of P application. Strengite was least effective in enhancing yield and P uptake by the crop.
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  • 12
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    Nutrient cycling in agroecosystems 46 (1996), S. 179-187 
    ISSN: 1573-0867
    Keywords: electrical conductivity ; leaching ; nitrogen ; pH ; phosphorus ; potassium ; release pattern ; slow-release fertilizers ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract We studied the effect of temperature on the release of N, P, and K from slow-release fertilizers (SRF). The study was conducted in micro-lysimeters filled with moist peat medium. Increasing the temperature from 4 to 12°C slightly increased N release from three different slow-release N (SRN) carriers with different particle sizes and coating thicknesses. At 21°C the rate of release was significantly different than the other two temperatures. Urea formaldehyde (UF), sulphur coated urea (SCU) and coated calcium nitrate (CCN), incubated in sphagnum moss peat, released between 3 and 20% of the applied N in six weeks. For eight synthetic and organic NPK carriers, the release pattern was similar to UF and SCU. However, the leaching losses of N from the NPK fertilizers were up to twenty times more than for the SRN products. Except for Osmocote® and Duna, which released 30–40% of the applied N as mineral-N within six weeks, all other slow-release and slowly mineralized NPK carriers acted like readily water-soluble compound NPK. Temperature did not affect the nutrient release from NPK fertilizers.
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  • 13
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    Nutrient cycling in agroecosystems 47 (1996), S. 243-250 
    ISSN: 1573-0867
    Keywords: fertilizer value ; nitrogen ; phosphorus ; poultry manure ; urea ; wetland rice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Poultry manure applied alone or in combination with urea at different N levels was evaluated as a N source for wetland rice grown in a Fatehpur loamy sand soil. Residual effects were studied on wheat which followed rice every year during the three cropping cycles. In the first year, poultry manure did not perform better than urea but by the third year, when applied in quantities sufficient to supply 120 and 180 kg N ha−1, it produced significantly more rice grain yield than the same rates of N as urea. Poultry manure sustained the grain yield of rice during the three years while the yield decreased with urea. Apparent N recovery by rice decreased from 45 to 28% during 1987 to 1989 in the case of urea, but it remained almost the same (35, 33 and 37%) for poultry manure. Thus, urea N values of poultry manure calculated from yield or N uptake data following two different approaches averaged 80, 112 and 127% in 1987, 1988 and 1989, respectively. Poultry manure and urea applied in 1:1 ratio on N basis produced yields in between the yields from the two sources applied alone. After three cycles of rice-wheat rotation, the organic matter in the soil increased with the amount of manure applied to a plot. Olsen available P increased in soils amended with poultry manure. A residual effect of poultry manure applied to rice to supply 120 or 180 kg N ha−1 was observed in the wheat which followed rice and it was equivalent to 40 kg N ha−1 plus some P applied directly to wheat.
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  • 14
    ISSN: 1573-0867
    Keywords: pasture fertilization ; phosphorus ; potassium ; nutrient budget ; nutrient efficiency
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Dairy farming is the main agricultural activity of the Basque Country. A dairy farm is characterized as a system with soils and crops, forage, cattle and manure as main components, and in such a system, nutrient cycling is very important to maintain soil fertility and optimize forage production. To quantify nutrient transfers in the cycle, a simple system was developed and has been applied to seventeen farms to examine its ability to achieve a balanced P and K fertilization. These farms have provided data on inputs (fertilizer, feeds, concentrates), pasture and manure management, and outputs (milk production), and soil samples have been taken from farm pastures. Phosphorus and K in excreta and uneaten pasture is used with a relatively high efficiency as suggested by the relatively high efficiency of P and K utilization by the pasture that usually ranges from 70 to 90%. Concentrate feeding (3000 kg cow−1 yr−1) represents one of the main P and K inputs in Basque Country dairy farms, averaging 26 and 66 kg ha−1, respectively. Besides, release of K in the soil through slow liberation from non-exchangeable sites was estimated as 30 kg ha−1. Thus, a high efficiency in excreta recycling would diminish substantially P and K mineral fertilizer needs. Farm nutrient budgets appear to be a convenient tool for determining nutrient shortages and surpluses at farm level, and thus they are considered as a first step to support a better management of maintenance fertilization of permanent pastures.
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  • 15
    ISSN: 1572-9729
    Keywords: bioavailability ; builders ; detergents ; kinetics ; mineralization ; sewage sludge ; soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Tetradecenyl succinic acid (TSA) is the major component of a detergent builder (C12-C14 alkenyl succinic acid), which is inherently biodegradable. 14C-TSA was dosed as a component of sewage sludge into a soil with a history of sludge amendment at final added concentrations of 1.5 and 30 mg (kg soil)-1. In addition, it was dosed to the soil in an aqueous solution to a final added concentration of 30 mg (kg soil)-1. Dose and form were found to have a pronouced effect on the mineralization kinetics. When dosed in a realistic form and concentration (i.e. 1.5 mg (kg soil)-1 as a component of sludge), TSA was mineralized at its highest rate and to its greatest extent, and the mineralization half-life was 2.4 days. When dosed at 30 mg (kg soil)-1 as a component of sludge, mineralization began immediately, and the half-life was 23 days. In contrast, when dosed at this concentration in aqueous solution, the onset of mineralization was preceded by a 13 day lag period and the mineralization half-life was 69 days. Primary biodegradation and mineralization rates of TSA were very similar. Approximately, half the radioactivity was evolved as 14CO2, while the remaining radioactivity became non-extractable, having presumably been incorporated into biomass or natural soil organic matter (humics). This study demonstrated that TSA is effectively removed from sludge-amended soils as a result of biodegradation. Furthermore, it showed the effect that dose form and concentration have on the biodegradation kinetics and the importance of dosing a chemical not only at a relevant concentration but also in the environmental form in which it enters the soil environment.
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  • 16
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    Biodegradation 7 (1996), S. 73-81 
    ISSN: 1572-9729
    Keywords: diesel oil ; biodegradation ; CSTR ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In batch culture diesel oil was degraded rapidly, with a maximum growth rate (for a consortium of microorganisms) of 0.55 h-1. The corresponding yield Y SX was 0.1 Cmol/Cmol. In a continuous stirred tank reactor the maximum dilution rate was about 0.25 h-1, with a yield of 0.3 Cmol/Cmol. With a residence time of 1 day 82% of the influent oil was degraded. In the batch reactor, of the mixture of linear and branched alkanes the linear alkanes were degraded fastest and with the highest yield. Only after most of the linear alkanes had disappeared were the branched alkanes consumed. In a CSTR a large part of the branched alkanes was not degraded.
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  • 17
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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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  • 18
    ISSN: 1432-1041
    Keywords: Key words Diphemanil methylsulphate ; Neonate; antimuscarinic agent ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
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  • 19
    ISSN: 1432-072X
    Keywords: Key words Auxostat ; Batch culture ; Chemostat ; Continuous culture ; Fermentation control ; Inhibition ; kinetics ; Nutristat ; On-line measurement ; Pentachlorophenol ; Pollutant ; Sphingomonas ; Steady-state conditions ; Toxicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A bacterium degrading pentachlorophenol (PCP) as the only source of carbon and energy was grown in a “nutristat”, i.e., a continuous culture with on-line measurement and control of the substrate concentration. We improved the PCP nutristat by incorporation of a personal computer with a proportional integral derivative (PID) algorithm for controlling the medium feed pump. The controlled value deviated from the average (set-point) value by 1% maximally. In the PCP nutristat (30°C), the steady-state dilution rate, and hence, specific growth rate, showed a maximum value of 0.142 ± 0.004 h–1 at set-point PCP concentrations between 37 and 168 μM. At PCP concentrations above 168 μM, the steady-state growth rate decreased because of inhibition. The growth yield coefficient was not seriously affected by the PCP concentration, suggesting that uncoupling was not the inhibitory mechanism. It was concluded that the PCP nutristat is very useful for establishing steady-state conditions that maintain growth-inhibitory PCP concentrations and high cell concentrations, conditions for which the chemostat is not suitable.
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  • 20
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    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Keywords: bone cement ; DSC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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  • 21
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    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Keywords: compensation effect ; DSC ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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  • 22
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    Journal of thermal analysis and calorimetry 47 (1996), S. 569-575 
    ISSN: 1572-8943
    Keywords: Bi2O3 ; CaCO3 decomposition ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Former studies concerning the formation of the compounds in the pseudobinary systems of Bi2O3-MO type (M =Ca, Sr, Ca+Sr) have shown that the reaction which occurs with the highest rate is that between Bi2O3 and CaO. In the present work CaCO3 was used as CaO source. We carried out an investigation of the thermal decomposition of CaCO3 in the presence of Bi2O3 in comparison with the decomposition of pure CaCO3. The presence of Bi2O3 exerts a complex influence on the CaCO3 decomposition acting on the nucleation as well as on the diffusion of CO2. The decomposition of the samples with low Bi2O3 content follows the mechanism of a contracting sphere. A change from surface nucleation to bulk nucleation is recorded for higher amounts of Bi2O3.
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  • 23
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1437-1450 
    ISSN: 1572-8943
    Keywords: browning ; crystallization ; glass transition ; kinetics ; milk powder ; water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An exotherm, observed in differential scanning calorimetry (DSC) scans of amorphous food materials above their glass transition temperature,T g, may occur due to sugar crystallization, nonenzymatic browning, or both. In the present study, this exothermal phenomenon in initially anhydrous skim milk and lactose-hydrolyzed skim milk was considered to occur due to browning during isothermal holding at various temperatures above the initialT g. The nonenzymatic, Maillard browning reaction produces water that in amorphous foods, may plasticize the material and reduceT g. The assumption was that quantification of formation of water from theT g depression, which should not be observed as a result of crystallization under anhydrous conditions, can be used to determine kinetics of the nonenzymatic browning reaction. The formation of water was found to be substantial, and the amount formed could be quantified from theT g measured after isothermal treatment at various temperatures using DSC. The rate of water formation followed zero-order kinetics, and its temperature dependence well aboveT g was Arrhenius-type. Although water plasticization of the material occurred during the reaction, and there was a dynamic change in the temperature differenceT−T g, the browning reaction was probably diffusioncontrolled in anhydrous skim milk in the vicinity of theT g of lactose. This could be observed from a significant increase in activation energy. The kinetics and temperature dependence of the Maillard reaction in skim milk and lactose-hydrolyzed skim milk were of similar type well above the initialT g. The difference in temperature dependence in theT g region of lactose, but above that of lactose-hydrolyzed skim milk, became significant, as the rate in skim milk, but not in lactose-hydrolyzed skim milk, became diffusion-controlled. The results showed that rates of diffusion-controlled reactions may follow the Williams-Landel-Ferry (WLF) equation, as kinetic restrictions become apparent within amorphous materials in reactions exhibiting high rates at the same temperature under non-diffusion-controlled conditions.
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  • 24
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    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
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  • 25
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1081-1091 
    ISSN: 1572-8943
    Keywords: kinetics ; thermal degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic study of thermal degradation takes into account the validity of the Arrhenius equation. From TG data, the activation energy,E a and pre-exponential factor,A, are evaluated. These results are interpreted by using the ‘kinetic compensation effect’ as basis. A linear correlation between In(A) andE a is obtained in all cases studied. However, in a plot of the logarithm of the rate constant as a function of reciprocal temperature for the same series of reactions, the thermal oxidative degradations of Nylon-6 and PVC display a point of concurrence and one isokinetic temperature, whereas those of HIPS and PC do not. Therefore, in the thermal oxidative degradations of Nylon-6 and PVC a ‘true’ compensation effect occurs, which could be related to the bulk properties of metal oxides, such as different valence states, whereas for other polymers it displays only an ‘apparent’ compensation effect. This means that degradation is largely independent of the bulk properties of oxides, but may be related to the distribution of different kinds of active links in the polymer surface having different activation energies.
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  • 26
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    Journal of thermal analysis and calorimetry 46 (1996), S. 49-54 
    ISSN: 1572-8943
    Keywords: kinetics ; solid-phase reactions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The convexity of localization forms, strictly required by conventional geometric-probabilistic formalism, is not in agreement with many experimental observations concerning solid-phase chemical reactions. In a discussion of the essence of this requirement, it is shown that it may be weakened for non-convex localization forms consistent with the symmetry of a solid reagent and described within the geometric-probabilistic approach in terms of planigons and Wigner-Seitz cells.
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  • 27
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    Journal of thermal analysis and calorimetry 46 (1996), S. 225-236 
    ISSN: 1572-8943
    Keywords: IR ; kinetics ; TG-DTG-DTA ; l,3,5-triamino-2,4,6-trinitrobenzene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) in condensed state has been investigated by high temperature infrared spectroscopy (IR) and thermogravimetry (TG) in conjunction with pyrolysis gas analysis, differential thermal analysis (DTA) and hot stage microscopy. The decomposition proceeds in two main stages under isothermal conditions and the initial stage involving about 24% loss in weight obeys Avrami-Erofe'ev equation (n= 1), and is governed by an activation energy (E) of 150.58 kJ·mol−1 and log(A in s−1) 12.06. The second stage corresponding to 24 to 90% loss in weight gave best fit for Avrami-Erofe'ev equation,n=2, withE=239.56 kJ·mol−1 and log(A in s−1) 19.88 by isothermal TG. The effect of additives, on the initial thermolysis of TATB has also been studied. Evolved gas analysis by IR showed that NH3, CO2, NO2, HCN and H2O are produced in the initial stage of decomposition. The decomposition in KBr matrix in the temperature range 272 to 311.5°C shows relative preferential loss in the -NH2 to -NO2 band intensity which indicates that the rupture of C-NH2 bond, weakened also by the interaction of the NH2 with the neighbouring NO2 group, appears to be the primary step in the thermolysis of TATB.
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  • 28
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    Journal of thermal analysis and calorimetry 46 (1996), S. 285-290 
    ISSN: 1572-8943
    Keywords: kinetics ; system FeSO4·7H2O-MnO2
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Processes which occur during the thermal treatment of system FeSO4·7H2O-MnO2 are of the interest for obtaining MnSO4, which can be easily soluted in water and separated from impurities in manganese slime in zinc metallurgy. Results of the experimental investigations of such processes are given in this paper. Kinetic parameters for the previously defined mechanism were determined using Borchardt and Daniels method.
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  • 29
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    Journal of thermal analysis and calorimetry 46 (1996), S. 377-385 
    ISSN: 1572-8943
    Keywords: crystallization ; drawing ; kinetics ; Kissinger ; Ozawa ; poly(ethylene terephthalate)
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The non-isothermal crystallization kinetics of hot drawn poly(ethylene terephthalate) films were studied using the Kissinger and Ozawa equations. The influence of the initial drawing on the crystallization kinetics was investigated. The values of the apparent activation energy and of the Avrami exponent indicates that the nucleation and growth of crystallites depend greatly on the stress submitted to the samples.
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  • 30
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1223-1238 
    ISSN: 1572-8943
    Keywords: dehydroxylation ; goethite ; hematite ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of dehydroxylation of synthetic aluminous goethite was studied using isothermal and non-isothermal thermogravimetry. The complete isothermal dehydroxylation can be described by the Johnson-Mehl equation with up to three linear regions in plots of lnln [1/(1−y)]vs. Int Kinetics for the initial stage of dehydroxylation changed from diffusion to first-order through the temperature range 190 to 260°C. The rate of dehydroxylation was reduced by Al-substitution and increased with temperature. Activation energy for dehydroxylation, calculated from the time to achieve a given dehydroxylation extent, varied depending on the extent of dehydroxylation and Al-substitution. Non-stoichiometric OH existed in goethite and some remained in hematite after the complete crystallographic transition.
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  • 31
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1271-1282 
    ISSN: 1572-8943
    Keywords: CrO3 ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The course of the non-isothermal decomposition of CrO3 in air was explored kinetically, by using a number of widely accepted methods. The credibility of the values obtained from a given kinetic parameter (the reaction order, the activation energy and the frequency factor) was justified on the grounds of (i) a multiple correlation coefficient, and (ii) the merits and demerits of the method adopted. The results obtained may help towards a characterization of the non-isothermal conditions under which the encountered decomposition events and products could be resolved. The study was motivated by the results of previous physicochemical characterization studies [1, 2], in which catalytically important intermediates CrOx(3〈x〈6) were structurally identified.
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  • 32
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1313-1324 
    ISSN: 1572-8943
    Keywords: kinetics ; polyester resin
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The isothermal and non-isothermal degradation of a typical styrenated phthalic acid-maleic acid-propylene glycol polyester were measured. Non-isothermal and isothermal kinetic analyses were performed on the various degradation steps observed. The values of the non-isothermal and the isothermal kinetic parameters are in good agreement.
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  • 33
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1671-1679 
    ISSN: 1572-8943
    Keywords: kinetics ; polycarbonate
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal degradation of poly(2,2′,-propane-bis-4-phenyl carbonate) or bisphenol A polycarbonate (PC) alone and in presence of metal oxide as additives have been discussed. Thermal degradation of PC in presence of metal oxide additives may be surface induced catalytic thermo-oxidative degradation. Some metal oxides retard thermo-oxidative degradation of PC.
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  • 34
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1657-1669 
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; differential scanning calorimetry ; kinetics ; lignite ; oxidation ; thermogravimetric analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.
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  • 35
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    Keywords: kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of some compounds derived from 5-phenylfuran-2,3-dione was studied. The thermoanalytical data relating to the decomposition steps and intermediates were completed with mass spectrometric analysis and infrared spectroscopy results. For some of the investigated reactions, the kinetic and structural data correlated satisfactorily.
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  • 36
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    Journal of thermal analysis and calorimetry 47 (1996), S. 247-258 
    ISSN: 1572-8943
    Keywords: ethylene (vinyl acetate) ; kinetics ; polymer
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethylene (vinyl acetate), EVA, is a copolymer which is thermally degraded at high temperatures, with acetic acid release at approximately 620 K. This release can be studied by using thermal methods, and in particular thermogravimetric analysis. The present work was focused on establishing the polymer weight loss with temperature in order to calculate the activation energy of the overall deacetylation process. To obtain the final results, a Mettler TC50 instrument coupled with a Mettler TC11 microprocessor was used. The activation energies of four different industrial EVA formulations were calculated. The results obtained by applying different kinetic methods reported in the literature agreed reasonably well; they were compared in order to select the best method of reporting EVA deacetylation results.
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  • 37
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1041-1062 
    ISSN: 1572-8943
    Keywords: kinetics ; polymerization
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The method of computer experiments can be successfully applied to radical polymerization with the inclusion of initiation, propagation and termination. The convenient PC-program ‘TAkin’ for non-linear estimation of the parameters of calorimetric and thermoanalytical experiments was applied for determination of the activation parameters of chain propagation and termination. The overall evaluation of three or more data sets was preferred. The determination of the kinetic parameters proceeds satisfactorily of the measured curves are strongly different, e.g. with a changed start temperature of modified application of batch and semi-batch technique, including acceptable experimental errors. Eight recommendations for laboratory experts are given.
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  • 38
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1063-1080 
    ISSN: 1572-8943
    Keywords: depolymerization ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The method of computer-experiments can be applied successfully on the radical depolymerization under inclusion of initiation, depropagation and termination. The comfortable PC-program ‘TA-kin’ for the non-linear estimation of parameters for TG- or DSC-experiments was applied to the determination of activation parameters of depropagation and termination. Therefore the overall-evaluation of three or more data sets is a prerequisite. The determination of kinetic parameters runs satisfactory if the measured curves are strongly different, e.g. by varying the heating rate, including acceptable experimental errors. Several recommendations for laboratory experts are given. A great support for a very sufficient estimation is the inclusion of simultaneous analysis of the radical concentration.
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  • 39
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1709-1718 
    ISSN: 1572-8943
    Keywords: kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Results are presented on the thermal behaviour of [Fe(III)2Cu(C2C4)2(OH)4(H2O)2] precursor of copper ferrite. An investigation of the decomposition steps and intermediates was followed by a non-isothermal kinetic analysis of the processable steps.
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  • 40
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1201-1213 
    ISSN: 1572-8943
    Keywords: calcium aconitate ; DTA ; EGA ; kinetics ; SEM ; TG/DTG ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition of calcium and dicalcium magnesium aconitate hydrates were studied by TG/DTG, DTA, EGA, SEM and other physico-chemical techniques. The decomposition proceeds in four stages: dehydration; oxidation of the carboxylic acid portion of the salt; complete fragmentation of the hydrocarbon portion; and finally, decarboxylation of the metal carbonate to the oxide. The crystal morphologies of the hydrate and anhydrous salts of each compound are very similar. Tricalcium aconitate consists of well-developed twinned crystals and stellate clusters intergrown with flat platy crystals. On the other hand, dicalcium magnesium aconitate crystals are monoclinic with well-developed pinacoidal faces. The activation energy,E d (43±2 kJ mol−1 water), calculated from Borchardt and Daniels' method, for the dehydration process of calcium aconitate trihydrate is of the same order of magnitude as some simple metal salt hydrates. The rate constant, kd increased from 0.04/min at 238°C to greater than 0.86/min at 295°C. It is concluded that the dehydration process is due to cation bound water.
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  • 41
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    Journal of thermal analysis and calorimetry 47 (1996), S. 445-452 
    ISSN: 1572-8943
    Keywords: catalysts ; catalyst activity ; catalyst deactivation ; DSC ; gas reactions ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Gas reactions, catalyzed by solid catalysts, can be measured by DSC. In the experimental set-up an open sample pan with catalyst (powder or pellet) is placed on the sample side of the DSC sensor. The reactive gas mixture flows through the cell and reacts on the catalyst surface. The heat effect, caused by this reaction, results into a DSC signal. The calibration procedure is described for quantitative evaluation of the DSC measurements. For illustration four different reaction systems are discussed.
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  • 42
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    Journal of thermal analysis and calorimetry 47 (1996), S. 535-542 
    ISSN: 1572-8943
    Keywords: cellulose ; kinetics ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The complexity of the phenomena which arise during the heating of the various substances seldom can be described by a single reaction kinetic equation. As a consequence, sophisticated models with several unknown parameters have to be developed. The determination of the unknown parameters and the validation of the models requires the simultaneous evaluation of whole series of experiments. We can accept a model and its parameters if, and only if we get a reasonable fit to several experiments carried out at different experimental conditions. In the field of the thermal analysis the method of least squares alone seldom can select abest model or abest set of parameter values. Nevertheless, the careful evaluation of the experiments may help in the discerning between various chemical or physical assumptions by the quality of the corresponding fit between the experimental and the simulated date. The problem is illustrated by the thermal de-composition of cellulose under various experimental conditions.
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  • 43
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    Molecular and cellular biochemistry 156 (1996), S. 93-100 
    ISSN: 1573-4919
    Keywords: rat liver nucleus ; oxalate binding protein ; histone III ; purification ; kinetics
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The rat liver nuclear oxalate binding protein was isolated, purified by anion and cation exchange column chromatography using Diethyl Amino Ethyl Sephadex, Carboxy Methyl Cellulose and Carboxy Methyl Sephadex C-50 ion exchangers. The purified oxalate binding protein was found to be H1B of H1 fraction of histories. Kinetic analysis of oxalate binding showed the presence of two affinity sites, one with Kd of 133.5 nM and Bmax of 40 pmoles and another with Kd of 262.5 nM and Bmax of 210 pmoles. The optimal oxalate binding was at pH 4.2 and at 28°C. The oxalate binding was specific and reversible and not due to ionic charge interaction. The IC50 of other dicarboxylates was higher than that of oxalate. EGTA had no effect on oxalate binding but di- and tri-carboxylate carrier inhibitors and thiol modifying agents significantly lowered the binding activity. Oxalate binding to histones was significantly reduced in the presence of DNA or nucleotides, but RNA had no effect. ATP completely inhibited the oxalate binding activity at 1 mM concentration. Different tissues exhibited oxalate binding showing ubiquitous nature. Calf thymus H1 showed maximal binding similar to liver histones.
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  • 44
    ISSN: 1573-4919
    Keywords: acetylcholinesterase ; kinetics ; inhibition ; methotrexate ; anticancer drugs ; human erythrocyte
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract This work addresses the kinetic analysis of the interaction of methotrexate (MTX) with human erythrocyte membrane-bound acetylcholinesterase (AChE, EC 3.1. 1.7). It was found that the MTX effect was independent of time of incubation with AChE before the addition of substrate which proves its reversible action. The IC50 was determined, by three methods, to be 0.73 mM. The Michaelis-Menten constant (Ks) for the hydrolysis of acetylthiocholine iodide (ASCh) by AChE was 0.13 mM in the control system, a value decreased by 30–61% in the MTX treated systems. The Vmax was 1.27μtmole/min/mg protein for the control system while it was decreased by 44–77% in the MTX treated systems. The Linexveaver-Buck plot, Dixon plot, and their secondary replots indicated that the nature of the inhibition was of the linear mixed type, i.e. uncompetitive and noncompetitive. The values of Ki(slope) and KI(tntecept) were estimated as 1.67 and 0.34 mM, respectively.
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  • 45
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    Journal of fluorescence 6 (1996), S. 165-168 
    ISSN: 1573-4994
    Keywords: Cation binding ; fluorescence decay ; kinetics ; binding constants ; Na,K-ATPase ; eosin Y
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    Topics: Physics
    Notes: Abstract Time-resolved fluorescence and binding studies have been carried out on Na,K-ATPase in the presence of the fluorescent dye eosin Y to obtain thermodynamic and kinetic parameters for the interaction of the enzyme with different cations. Eosin Y binding is indicated by a 3 ns fluorescence decay process and is observed only in the presence of mono- and divalent cations. This type of cation binding is interpreted as a nonselective electrostatic interaction, with negatively charged groups of the enzyme providing a high-affinity eosin Y binding site. Eosin Y binding is observed only under conditions where the enzyme exists in the conformational state F1. The kinetic parameters of eosin Y binding have been determined employing stopped-flow fluorometry.
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  • 46
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    The protein journal 15 (1996), S. 631-637 
    ISSN: 1573-4943
    Keywords: Aminocyclase ; denaturation ; inactivation ; conformation ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The inactivation and unfolding of aminoacyclase (EC 3.5.1.14) during denaturation by different concentrations of trifluoroethanol (TFE) have been studied. A marked decrease in enzyme activity was observed at low TFE concentrations. The kinetic theory of the substrate reaction during irreversible inhibition of enzyme activity described previously by Tsou [Tsou (1988),Adv. Enzymol. Related Areas Mol. Biol. 61, 381–436] was applied to study the kinetics of the inactivation course of aminoacyclase during denaturation by TFE. The inactivation rate constants for the free enzyme and substrate-enzyme complex were determined by Tsou's method. The inactivation reaction was a monophasic first-order reaction. The kinetics of the unfolding course were a biphasic process consisting of two first-order reactions. At 2% TFE concentration, the inactivation rate of the enzyme was much faster than the unfolding rate. At a higher concentration of TFE (10%), the inactivation rate was too fast to be determined by conventional methods, whereas the unfolding course remained as a biphasic process with fast and slow reactions occurring at measurable rates. The results suggest that the aminoacyclase active site containing Zn2+ ions is situated in a limited and flexible region of the enzyme molecule that is more fragile to the denaturant than the protein as a whole.
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  • 47
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    Russian chemical bulletin 45 (1996), S. 2760-2762 
    ISSN: 1573-9171
    Keywords: chemiluminescence ; kinetics ; xenon trioxide ; europium(II,III) ions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Chemiluminescence has been observed in the reduction of perchloric aqueous solutions of XeO3 with Eu2+ ions, Fast (several seconds) consumption of EuII occurs when the ratio of the initial concentrations of the reactants (Eu2+]0 : [XeO3]0 〈 6; however, the chemiluminescence remains sufficiently bright and prolonged (up to −10 min after nearly complete oxidation of EuII to EuIII). The assumption was made that intermediates in the reduction of XeO3 participate in the chemiluminescent stages of the process.
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  • 48
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    Russian chemical bulletin 45 (1996), S. 328-334 
    ISSN: 1573-9171
    Keywords: vapor nitration ; cellulose ; nitric anhydride ; kinetics ; diffusion constant
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of vapor nitration of cellulose with nitric anhydride at various pressures was studied under conditions of natural convection in the absence of air, using the nonisothermal kinetic method. The process rate was found to be proportional to the N2O5 pressure. The nitration is described by a law of the dη/dt =k 1/(1+βν) type, wherek 1 = 103.82±0.5 exp[-(36000±(RT)]p N 2O5 s−1. β = 10−7.33±1.4exp[(41300±8000)/(RT)] s−1, s−1, within the extents of conversion from 0.04 to 0.4. At high levels of conversion, the nitration occurs with autoacceleration caused by the accumulation of the HNO3 formed. The diffusion mechanism of vapor nitration of cellulose was suggested and discussed. The values of the effective diffusion constant for N2O5 in cellulose and the corresponding activation energy (38.4±2.8 kJ mol−1) have been estimated.
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  • 49
    ISSN: 1573-9171
    Keywords: complex formation ; kinetics ; sodium dodecyl sulfate ; copper(II) ; 2-dimethylaminomethylphenol
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of the anionic surfactant sodium dodecyl sulfate on complex formation of 2-dimethylaminomethylphenol (1) with copper(u) in aqueous solutions and on the kinetics of the reactions of copper(n) complexes of 1 with 4-nitrophenylbis(chloromethyl)phosphinate (2) were studied. The reactivities of the complexes in these reactions are higher than that of 1 at all concentrations of SDS studied (0.010–0.200 mol L−1 with pH 7–9.
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  • 50
    ISSN: 1573-9171
    Keywords: unsaturated nitroxyl radicals ; secondary amines ; addition ; kinetics ; mechanism
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Routes for the reaction of a conjugated methylene group of nitroxyl radicals (NR) with secondary amines were suggested and analyzed. Kinetic parameters of the limiting step of this reaction for the NR-amine and diamagnetic analog of NR-amine systems were estimated. The effect of the medium on these reactions was examined. The specific behavior of polyethyleneimine in the reaction with activated methylene groups of 2,2,6,6-tetra methyl-3, 5-dimethylene-4-oxopiperidine-i-oxyl was demonstrated.
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    Russian chemical bulletin 45 (1996), S. 871-874 
    ISSN: 1573-9171
    Keywords: Kharash reaction ; catalysis ; iron pentacarbonyl ; kinetics ; thermal stability ; thermal reaction with CCl3X (X = Br, Cl) ; effect of olefin and DMF
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Fe(CO)5 is sufficiently stable at 80 °C in benzene solution and its thermal decomposition is not accelerated in the presence of phenyl cinnamate or/and DMF. The decomposition is accelerated by CCl3Br (drastically) and by CCl4 (to a lesser extent). DMF accelerates the reaction of Fe(CO)5 with CCl4. The (FeCl(DMF)5]2+[Cl3FeOFeCl3]2− complex has been isolated as a product; its composition and structure have been determined by X-ray analysis. The obtained data indicate the absence of coordination of DMF or/and an olefin with Fe0 species at the stage preceding oxidation. The mechanisms of the generation of CCl3 radicals in thermal and photochemical Kharash reactions in the presence of Fe(CO)5 are basically different. The probable pathways of the effect of DMF on the rate of the oxidative decomposition of Fe(CO)5 are discussed.
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  • 52
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    Russian chemical bulletin 45 (1996), S. 1875-1878 
    ISSN: 1573-9171
    Keywords: 2,4,6-trinitrotoluene ; thermal decomposition ; solvent effect ; chain mechanism ; dissociation energy of C-H bond ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate constants for the thermal decomposition of 2,4,6-trinitrotoluene have been measured in toluene and other hydrocarbon solvents. The initial, observed rate constant (k i) increases with dilution with toluene. The concentration dependence is described by the chain decomposition scheme with the transfer of the free valence to a solvent molecule. The activation energy and logk i were found to linearly correlate with the dissociation energy of the C-H bond of the solvent.
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  • 53
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    Russian chemical bulletin 45 (1996), S. 1879-1882 
    ISSN: 1573-9171
    Keywords: cellulose ; nitration ; nitric acid ; kinetics ; diffusion coefficient
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The regularities of vapor-phase nitration of cellulose with HNO3 under conditions of natural convection and hindered heat removal in the absence of air were studied using the nonisothermal kinetic method. It was established that the nitration rate at the depth of conversion of 0.08 to 0.7 is described by the kinetic law dη/dt =k 1 p/(1+βη), wherek 1 = 104.49±0.6 exp(−A/RT) s−1 atm−1, β = 10−35.5±15.7exp(B/RT),A = 36.6±3.8 kl mol−1, andB = 203±88 kJ mol−1. The diffusion mechanism of vapor-phase nitration of cellulose, which explains the high value of activation energies, is discussed. The effective diffusion coefficient of HNO3 in cellulose at 25 °3.7 · 10−7 cm2 s−1) and the activation energy of diffusion (38.3±4.2 kJ mol−1) were estimated.
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  • 54
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    Russian chemical bulletin 45 (1996), S. 1883-1888 
    ISSN: 1573-9171
    Keywords: decane ; nitric acid ; nitrogen dioxide ; oxidation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the reaction of decane with nitric acid (25.07–75.53 %) at 57.8 to 119 °C in an acid-decane-gas triphasic system was studied. The main contribution to the rate of heat release is made by the oxidation of decane with nitrogen dioxide in the organic phase proceedingvia the mechanism of a degenerate branched-chain reaction. Nitration plays the role of a chain termination reaction. The acid phase is the source of NO2, whose content increases with oxidation. The equilibrium of the nitrogen dioxide distribution in the triphasic system was analyzed. The kinetic law of the reaction, the dependences of the reaction constants of the initial and catalytic stages on temperature and the acid phase composition were determined. The results allow one to calculate the rate of heat release in the decane-HNO3 system under any conditions of the process.
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  • 55
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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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  • 56
    ISSN: 1573-5125
    Keywords: Eutrophication ; nutrients ; phosphorus ; nitrogen ; chlorophyll-a ; primary production ; secondary production ; Mytilus edulis ; river Rhine ; Wadden Sea ; North Sea
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract From 1955 to the mid 1980s the loads of both nitrogen and phosphorus from the river Rhine to the Dutch coastal area, the Wadden Sea included, increased. Since 1985 the phosphorus loads has decreased significantly, while the nitrogen load remained about the same. Annual primary production in the western Dutch Wadden Sea has increased fromc. 40 g C m−2 (1950) to 150 (mid 1960s) and over 500 g C m−2 (1986). The biomass of macrozoobenthos has more than doubled since 1970. Simultaneously, the meat yield of cultured blue mussels (Mytilus edulis), has increased since the 1960s. Previously, it was indicated that the increase in primary production of the phytoplankton over the period 1950 to 1986 was stimulated by the load of dissolved inorganic phosphate from Lake IJssel, a reservoir supplied by Rhine water. Since 1990, however, primary production has been higher than was expected from decreased phosphate loads from Lake IJssel. It is argued that this lack of response may have been caused by increased concentrations of dissolved inorganic phosphate at sea originating from increased inflow from a.o. the Strait of Dover, which compensate for the decrease in phosphate from the rivers, possibly in combination with a significant improvement of the light conditions of the water in the Wadden Sea.
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  • 57
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    Hyperfine interactions 101-102 (1996), S. 155-162 
    ISSN: 1572-9540
    Keywords: muon ; muonic hydrogen ; muonic molecule ; deuterium ; tritium ; fusion ; solid target ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The emission of µd and µt atoms from multilayer solid targets consisting of the mixtures of hydrogen isotopes has been investigated with a kinetics model. The methods to study the elastic scattering of muonic atoms, muon transfer, and molecular formation reactions with µ-atomic beams are discussed.
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  • 58
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    Hyperfine interactions 101-102 (1996), S. 163-167 
    ISSN: 1572-9540
    Keywords: muon ; muonic hydrogen ; energy distribution ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The kinetics of muonic atoms of hydrogen isotopes in an axially symmetric trap is studied. The problem of the determination of the initial kinetic energy distribution of µp and µd atoms from time-of-flight spectra is discussed. The effects of the scattering of muonic atoms from gas and of the stopping distribution are evaluated. When the collision length is much larger than the target radius, the moments of the kinetic energy distribution are shown to be determined by the time-of-flight spectrum in a model-independent way.
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  • 59
    ISSN: 1573-0778
    Keywords: hybridomas ; serum-free medium ; monoclonal antibodies ; reactor series ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Hybridomas were cultured under steady-state conditions in a series of two continuous stirred-tank reactors (CSTRs), using a serum-free medium. The substrate not completely converted in the first CSTR, was transported with the cells to the second one and very low growth rates, high death rates, and lysis of viable cells were observed in this second CSTR. These conditions are hardly accessible in a single vessel, because such experiments would be extremely time-consuming and unstable due to a low viability. In contrast to what is often observed in literature, kinetic parameters could thus be derived without the neccessity for extrapolation to lower growth rates. Good agreement with literature averages for other hybridomas was found. Furthermore, showing that the reactor series is a valuable research tool for kinetic studies under extreme conditions, the possibility to observe cell death under stable and defined steady-state conditions offers interesting opportunities to investigate apoptosis and necrosis. Additionally, a model was developed that describes hybridoma growth and monoclonal antibody production in the bioreactor cascade on the basis of glutamine metabolism. Good agreement between the model and the experiments was found.
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  • 60
    ISSN: 1573-5117
    Keywords: river ; hyporheic ; dissolved organic carbon ; nitrogen ; phosphorus ; silica
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    Topics: Biology
    Notes: Abstract Solute, nutrient and bacterial inputs to the River Rhône from the interstitial habitat of a gravel bar and the floodplain aquifer were investigated during an artificial drought. Eight springs were investigated: four groundwater-fed springs in the floodplain, located at the bottom of the bank; and four interstitial-fed springs located at the downstream end of a gravel bar. During this period, the inflows of groundwater to the river represented an average input of 0.77 mg l−1 of nitrogen (of which 93.3% were nitrates), 0.0187 mg l−1 of total phosphorus (of which 42.2% was orthophosphate), 3.56 mg l−1 of silica, 2.315 ± 0.703 mg l−1 of dissolved organic carbon (DOC, of which 47% was biodegradable) and 7.3 × 104 ± 3.7 × 104 bacteria per ml (of which 8.8% were active). Silica, DOC, biodegradable DOC, and bacteria concentrations displayed temporal variations during the study, which seem to be linked to the biological activity of the groundwater biofilm. There was a strong heterogeneity between the two types of groundwater that flow to the river: concentrations of calcium and alkalinity were higher in bank springs than in gravel bars springs. In these latters, sulfate, sodium, nitrogen, phosphorus were significantly higher.
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  • 61
    ISSN: 1573-5117
    Keywords: Loosestrife ; Lythrum salicaria ; cattail ; decomposition ; phosphorus ; wetland
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    Topics: Biology
    Notes: Abstract Purple Loosestrife is rapidly displacing native vegetation in North American wetlands. Associated changes in wetland plant communities are well understood. Effects of Loosestrife invasion on nutrient cycling and decomposition rates in affected wetlands are unknown, though potentially of significance to wetland function. We used litter bag methods to quantify decomposition rates and phosphorus concentrations of purple Loosestrife (Lythrum salicaria) and native cattails (Typha spp.) in fourteen Minnesota wetlands. A 170-day study that began in autumn modeled decomposition of Loosestrife leaves. Loosestrife stems andTypha shoots that had overwintered and fragmented were measured in a 280- day study that began in spring. In general, Loosestrife leaves decomposed most rapidly of the three;Typha shoots decomposed faster than Loosestrife stems. Significant decay coefficients (k-values) were determined by F-testing single exponential model regressions of different vegetation types in the fourteen wetlands. Significant decay coefficients were:k = 2.5 × 10−3 and 4.32 × 10−3 for all Loosestrife leaves (170 d);k = 7.2 × 10−4 and 1.11 × 10−3 for overwintered Loosestrife stems (280-d) andk = 7.9 × 10−4, 1.42 × 10−3 and 2.24 × 10−3 for overwinteredTypha shoots (280-d). Phosphorus concentrations of plant tissue showed an initial leaching followed by stabilization or increase probably associated with microbial growth. Loosestrife leaves had twice the phosphorus concentration of Loosestrife stems andTypha shoots. Our results indicate that conversion of wetland vegetation from cattails to Loosestrife may result in significant change in wetland function by altering timing of litter input and downstream phosphorus loads. Conversion of a riverine, flow- through wetland fromTypha to Loosestrife may effectively accelerate eutrophication of downstream water bodies. Impacts of Loosestrife invasion must be considered when wetlands are managed for wildlife or for improvement of downstream water quality.
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  • 62
    ISSN: 1573-5117
    Keywords: Sediment ; nitrogen ; phosphorus ; regeneration ; iron availability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract During 1994 net sediment-water fluxes of oxygen, ammonium and inorganic phosphorus as well as sediment profiles of organic matter, nitrogen, phosphorus and iron were determined in three shallow eutrophic environments. Investigations were conducted monthly from March to December at five stations in the Sacca di Goro (Po River Delta, Italy). In the late summer, samples were collected from a single site in the Prévost lagoon (French Mediterranean coast) and three stations in the Bassin d'Arcachon (French Atlantic coast). In the Sacca di Goro, water-sediment exchanges of O2, NH 4 + and PO 4 3− were estimated by means of core incubation in the dark. Benthic fluxes for the French lagoons were in part determined experimentally using benthic chambers and in part from the literature. In general in the Sacca di Goro the highest oxygen uptake and nutrient release rates were found at the central sites, affected by macroalgal growth. At the sampling site adjacent to the freshwater inlet, sediment-water exchanges were principally influenced by tidal activity. In terms of organic matter and nutrient levels, sediments from the Sacca di Goro and from the Prévost lagoon, both colonised by the floating macroalga Ulva rigida C. Agardh, were similar. Sediments from the inner sheltered site in the Bassin d'Arcachon, invaded by the rooted macrophyte Ruppia cirrhosa (Pet.) Grande, showed the highest total N and P content (363 ± 157 µmol N cm−3 and 15 ± 2 µmol P cm−3 as average values in the top 10 cm of sediment), but were low in pore water ammonium and orthophosphate probably due to the high sequestering capacity of the system and/or efficient coupling between bacterial nutrient regeneration and assimilation by the plant roots. In addition the outer tidal stations in the Bassin d'Arcachon, invaded by rooted macrophytes, were low in pore water nutrients. A different trend was evident in the Prévost lagoon where the concentrations of exchangeable inorganic phosphorus and ammonium were appreciable (0.28 ± 0.07 µmol P cm−3 and 2.4 ± 1.4 µmol N cm−3 as average values in the top 10 cm of sediment). High amounts of dissolved organic nitrogen were found in the pore water at all the sites investigated showing the key role of the organic nitrogen in the recycling of nitrogen in these systems. The hypothesis that iron is a key factor in controlling phosphorus release is discussed since the Sacca di Goro, which is subject to dystrophic crises, is richer in iron than the Bassin d'Arcachon, which is a more buffered system.
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  • 63
    ISSN: 1573-5117
    Keywords: blue-green algae ; recruitment ; sediment ; phosphorus ; alum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The sediment-to-water recruitment of blue-green algae was investigated in a shallow lake following treatment with aluminum sulfate and sodium aluminate to control sediment phosphorus (P) release. A comparison of results from two summers each before and after treatment indicates that the treatment did not universally impact the recruitment of either sporulating or non-sporulating forms of blue-green algae. Blooms of Anabaena, Aphanizomenon, and Coelosphaerium resulted predominantly from growth in the water column following strong recruitment episodes lasting up to two weeks, while Microcystis populations were relatively insensitive to periodically high inputs from recruitment. The development of planktonic populations of Gloeotrichia echinulata, by contrast, were largely dependent on sustained recruitment in response to adequate light and temperature regimes at the sediment surface. The cellular P content of recruited G. echinulata colonies was unaffected by the accumulation of aluminum floc to the lake sediments. Both G. echinulata and C. naegelianum showed elevated levels of cellular P in newly recruited colonies as compared to planktonic colonies, indicating P transport from the sediments to the water column. Total P translocation by blue-green algae was negligible in the absence of a substantial recruitment of G. echinulata. The recruitment of G. echinulata, and hence the magnitude of P translocation, was therefore more responsive to environmental conditions prevalent at the sediments than to direct effects of the treatment itself.
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  • 64
    ISSN: 1573-5117
    Keywords: Ulva rigida ; growth rates ; nitrogen ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Growth of the seaweed Ulva rigida C. Agardh was investigated in relation to biomass densities, internal nutrient pools and external nutrient supply. Research was carried out from 23 March to 5 July 1994 in the Sacca di Goro (Po Delta, Northern Italy), whose south-eastern part was covered by extensive mats of Ulva rigida. Two types of field experiments were conducted by incubating Ulva thalli inside large cages. In the first experiment, beginning on 23 March, 100 g of wet thalli were placed into the cages, allowed to grow for two weeks, then collected and replaced. This procedure was repeated 8 times over the study period. In the second experiment, Ulva thalli were left inside the cages and collected at selected time intervals (14, 27, 41, 64 and 76 days) in order to simulate the effects of increased density on growth and nutrient storage. We recorded specific growth rates (NGR) ranging from 0.025 to 0.081 d−1 for a period up to two months in the repeated short-term experiments performed at relatively low initial algal densities (300–500 g AFDW m−3). These NGR resulted significantly related to dissolved inorganic nitrogen (DIN) in the water column. Tissue concentrations of total Kjeldahl nitrogen (TN) were almost constant, while extractable nitrate decreased in a similar manner to DIN in the water column. Total phosphorus showed considerable variation, probably linked to pulsed freshwater inflow. In the long-term incubation experiment, NGR of Ulva was inversely related to density. Internal concentrations of both total P and TN reached maximum values after one month; thereafter P concentration remained almost constant, while TN decreased below 2% w/w (by dry weight). The TN decrease was also accompanied by an abrupt decrease in nitrate tissue concentration. The biomass incubated over the two month period suffered a progressive N limitation as shown by a decreasing NY ratio (49.4 to 14.6). The reciprocal control of Ulva against biogeochemical environment and viceversa is a key factor in explaining both resource competition and successional stages in primary producer communities dominated by Ulva. However, when the biomass exceeds a critical threshold level, approximately 1 kg AFDW m−3, the macroalgal community switches from active production to rapid decomposition, probably as a result of selfshading, biomass density and development of anaerobic conditions within the macroalgal beds.
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  • 65
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    Hydrobiologia 322 (1996), S. 129-136 
    ISSN: 1573-5117
    Keywords: Lake Ladoga ; phosphorus ; sediment ; pore water ; phosphorus release ; internal phosphorus loading
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Sedimentary phosphorus fractions and phosphorus release from the sediments were studied in Lake Ladoga at altogether 46 sampling sites, representing the full range of sediment types encountered in the lake. Determination of P fractions and physico-chemical analyses were made of surface sediment cores (10–20 cm long, each sampled at 3–4 levels) and in the overlying water. The range of total phosphorus per dry weight of sediment was 0.2–3.3 mg g−1, and that of inorganic P 0.1–2.5 mg g−1. The levels of interstitial soluble phosphorus, range 2–613 µg 1−1 for total P and 1–315 µg 1−1 for inorganic P, were higher than those of dissolved P concentrations in the overlying water. Diffusive fluxes of phosphate from sediment to the overlying water were estimated using three independent methods. The estimated range was 4–914 µg P m−2 d−1; the mean value for the whole bottom area, 0.1 mg P m−2 d−1, is lower than previously published estimates. The estimated annual contribution of sedimentary inorganic P flux to Lake Ladoga water is equal to 620 tons of P per year, which amounts to more than 10% of the estimated external P load into the lake. 68% of the total diffusive flux emanates from deep water sediments, which are not exposed to seasonal variation of conditions. In deep lakes, such as Lake Ladoga, phosphorus release from the sediments is controlled primarily by diffusive mechanisms. Wave action and currents as well as bioturbation are probably of importance mainly in shallow near-shore areas. Phosphorus release by gas ebullition and macrophytes is considered negligible.
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  • 66
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    Hydrobiologia 334 (1996), S. 169-183 
    ISSN: 1573-5117
    Keywords: Oligochaete ; eutrophication ; large-scale experiment ; ditch ; phosphorus ; nitrogen ; oxygen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Eight experimental ditch mesocosms were used to study the effect of eutrophication over four years. The experimental ditches had a sand or clay bottom. The ditches were treated with additions of phosphorus, phosphorus and nitrogen, or without additions (controls). Oligochaetes were sampled by deploying trays with substratum for colonization over twenty weeks. Both the important variables phosphorus, nitrogen and oxygen as well as the oligochaete species and numbers are presented. The effects of nutrient additions on phosphorus, nitrogen and oxygen concentrations were described together with changes in oligochaete species composition and numbers. The results were further analyzed by redundancy analysis (RDA). In the clay-lined ditches nutrient addition coincided with fluctuation in oxygen concentration. The higher the nutrient addition levels the longer the period of oxygen depletion became. During oxygen depletion the number of oligochaetes was strongly reduced or even became zero. The low nutrient status of the sandy bed in the sand-lined ditches slowed down the rate of colonization. Only a few tubificids were collected. Eutrophication effects were only observed at the highest nutrient addition level. Considerable variation is attributed to stochastic factors in the sand-lined ditches. Whether oligochaete species were present was related to the length of the colonization period. The substratum composition and food together with oxygen regime decided whether they become more or less abundant in ditches. Large-scale mesocosm experiments require time to develop. Only after the first colonization period variables of species presences and abundances can be employed to detect changes associated with eutrophication. Oligochaetes can be used to measure colonization as well as eutrophication processes.
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  • 67
    ISSN: 1573-5117
    Keywords: nitrogen ; phosphorus ; chlorophyll ; organic matter ; mountain lakes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Concentrations of total phosphorus (TP), inorganic and organic nitrogen, organic matter, and chlorophyll-a were studied in ten mountain lakes at various stages of acidification, trophy, and type of watershed during each July and October from 1987 to 1990. Concentrations of TP and total organic matter were higher in July than in October. Concentrations of NH44 +-N decreased and NO3 −-N increased from July to October. The relative composition of total nitrogen (TN) and its concentration were strongly dependent on the type of watershed: the lowest TN concentrations were observed in lakes with forested watersheds, increasing above the timberline and reaching maximum values in acidified lakes with rocky watersheds. In the pool of TN, nitrate was most important in lakes above the timberline (70–86% of TN), and organic nitrogen in forest lakes (〉 90% of TN). Lakes with rocky watersheds were characterized by high ratios of TN:TP (〉 250 by mass). The concentration of chlorophyll-a varied widely, from 0.01 to 22.6 µg l−1, without any consistent change between July and October, and were P limited.
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  • 68
    ISSN: 1573-5117
    Keywords: phytoplankton ; zooplankton ; phosphorus ; aquatic mesocosms ; trophic interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Eight cylindrical enclosures (3 m diameter, 2.7 m long, V = 20m3) were installed in eutrophic Rice Lake (Ontario, Canada) in late spring of 1987. Fish (yearling yellow perch (Perca flavescens) and macrophytes (Potamogeton crispus) presence and absence were set at the beginning of the experiment to yield four combinations of duplicate treatments. The purpose of the experiment was to determine if the phytoplankton, zooplankton, macrophytes and fish species resident in the lake interact to influence water quality (major ions, phosphorus, algal densities and water clarity). The presence of fish was associated with: (1) decreased biomass of total zooplankton, (2) decreased number of species in the zooplankton, (3) decreased average size of several zooplankton taxa, (4) higher total phosphorus concentrations, (5) higher phytoplankton and chlorophyll a concentrations, (6) lower water clarity, (7) lower potassium levels during macrophyte die-back, (8) lower pH and higher conductivity in the presence of macrophytes. Biomass of large Daphnia species (but not total zooplankton) was highly correlated with the algal response (r 2 = 0.995) and was associated with reduced biomass of several algal taxa including some large forms (Mougeotia, Oedogonium) and several colonial blue-green algae. However, no significant control of late summer growth of the bloom-forming blue-green alga Anabaena planctonica Brun. was achieved by the Daphnia presence-fish absence treatment. Release of phosphorus to the water column during the die-back of P. crispus was not an important phenomenon.
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    Hydrobiologia 322 (1996), S. 241-248 
    ISSN: 1573-5117
    Keywords: water chemistry ; phosphorus ; nitrogen ; intercalibration ; Lake Ladoga ; large lake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract As part of the Russian-Finnish research studies on Lake Ladoga, joint expeditions were organized in 1992 and 1993. Water samples were collected for intercalibration of chemical analysis methods and to monitor the chemical quality of the lake water. In August of 1992 water samples were taken from northern Lake Ladoga for intercalibration of Russian and Finnish analysis methods. In August 1993 water samples were collected from 23 sampling stations in all parts of the lake; some of these were also used for intercalibration purposes. The oxygen, colour and CODMn results were at the same level in the intercalibration. In 1993, the Ptot results obtained were acceptable. In Ntot, Fe and Mn analysis there seemed to be systematic and random errors between some results. The Secchi depth ranged from 1.5 m to 3.3 m. The average concentrations for the total phosphorus ranged from 15 µg 1−1 to 29 µg 1−1. The total nitrogen values were from 620 µg 1−1 to 690 µg 1−1. The N:P ratio varied from 24 to 40. The concentration of phosphorus indicated mesotrophic or even eutrophic conditions in the lake. Phosphorus seemed to be the limiting nutrient to bacteria and algae.
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  • 70
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    Journal of pharmacokinetics and pharmacodynamics 24 (1996), S. 19-44 
    ISSN: 1573-8744
    Keywords: indocyanine green ; hepatic removal ; liver function test ; organic anions ; kinetics ; protein binding ; physiologically based pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Indocyanine green (ICG) is used in cardiology and hepatology for the estimation of cardiac output, liver function, and splanchnic blood flow. ICG is bound to plasma proteins and ultimately excreted by the liver. We studied the whole body kinetics of ICG during constant infusion in pigs weighing 30–40 kg. The conventional kinetic model (backflux model) assumes that deviations from one-compartmental linear kinetics is caused by backflux from a liver storage to plasma, and that no extravascular, extrahepatic distribution takes place. This model was tested against an alternative (redistribution) model postulating that temporary redistribution of ICG into an extrahepatic extravascular storage was responsible for the deviations while the hepatic uptake was a one-way first-order process. A mathematical analysis of the two models showed that they predicted different time courses of the hepatic extraction fraction of ICG. Thus, with blood sampling from both a peripheral artery and a hepatic vein, a discriminative model-testing experiment was possible. This test required a first-order steady-state hepatic removal of ICG which was confirmed in 7 experiments with infusion rates varied in a stepwise fashion (0.133±0.003, 0.269±0.010, 0.547±0.020 and 0.130±0.003 μmol·min1). In the model-testing experiments (n=10) ICG was infused at a constant rate of 0.135±0.007 μmol·min1. The mean concentration in peripheral artery (μM) was well fitted by the biexponential functionC(t)=0.476·(1–0.632·e0.216–1−0.368·e0.0172–1). The time course of the observed hepatic extraction fraction was significantly different (p=0.004) from that predicted from the backflux model but in agreement (p=0.98) with the new model assuming hepatic removal to be a one-way process and implying temporary ICG redistribution into an extrahepatic, extravascular storage with an apparent volume of 0.144±0.023 L·Kg1. Accordingly, extravascular ICG was demonstrated in a number of different tissues after 4-hr infusion (n=3). If ICG is used to estimate hepatic blood flow according to Fick's principle, the use of a backflux model to correct for non-steady-state conditions will lead to an overestimation of hepatic blood flow of 28% after 25-min infusion, 16% after 50 min, and 6% after 100 min. The study indicated that distribution of ICG between plasma and tissues is not instantaneous, and that the time course of the redistribution itself significantly influences whole body kinetics. Comparison with a previously published study by Ott, Keiding, and Bass of ICG kinetics after bolus injection suggested that a two-compartment model was insufficient and that the kinetics for the exchange of ICG between plasma and the redistribution space may be nonlinear. The study demonstrates how blood sampling on both sides of the eliminating organ can expose the influence of redistribution. The discriminative model test for constant infusion experiments is novel and may be useful with other ligands.
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    Wetlands ecology and management 4 (1996), S. 177-187 
    ISSN: 1572-9834
    Keywords: nitrogen cycling ; phosphorus ; wetland ; succession
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We compared the mechanisms of nitrogen (N) and phosphorus (P) removal in four young (〈15 years old) constructed estuarine marshes with paired mature natural marshes to determine how nutrient retention changes during wetland ecosystem succession. In constructed wetlands, N retention begins as soon as emergent vegetation becomes established and soil organic matter starts to accumulate, which is usually within the first 1–3 years. Accumulation of organic carbon in the soil sets the stage for denitrification which, after 5–10 years, removes approximately the same amount of N as accumulating organic matter, 5–10 g/m2/yr each, under conditions of low N loadings. Under high N loadings, the amount of N stored in accumulating organic matter doubles while N removal from denitrification may increase by an order of magnitude or more. Both organic N accumulation and denitrification provide for long-term reliable N removal regardless of N loading rates. Phosphorus removal, on the other hand, is greatest during the first 1–3 years of succession when sediment deposition and sorption/precipitation of P are greatest. During this time, constructed marshes may retain from 3 g P/m2/yr under low P loadings to as much as 30 g P/m2/yr under high loadings. However, as sedimentation decreases and sorption sites become saturated, P retention decreases to levels supported by organic P accumulation (1–2 g P/m2/yr) and sorption/precipitation with incoming aqueous and particulate Fe, Al and Ca. Phosphorus cycling in wetlands differs from forest and other terrestrial ecosystems in that conservation of P is greatest during the early years of succession, not during the middle or late stages. Conservation of P by wetlands is largely regulated by geochemical processes (sorption, precipitation) which operate independently of succession. In contrast, the conservation of N is controlled by biological processes (organic matter accumulation, denitrification) that change as succession proceeds.
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  • 72
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    Wetlands ecology and management 4 (1996), S. 199-206 
    ISSN: 1572-9834
    Keywords: constructed wetlands ; wastewater ; macrophytes ; nitrogen ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The first full-scale constructed wetland (CW) in the Czech Republic was built in 1989 and there are now three tertiary systems and 50 secondary treatment facilities. We report here on the design and operational efficiencies of these facilities. All CWs have been designed with horizontal subsurface flow. Coarse sand, gravel and crushed stones with size fraction of 4–16 mm are commonly used as substrates. The area of vegetated beds ranges between 18 and 4500 m2 and operational CWs are designed for population equivalent (PE) of 4 to 1,100. Common reed (Phragmites australis) is the most frequently used macrophyte species. Results from systems studied during 1994 and 1995 show that the effluent concentrations of organics and suspended solids (SS) are well below the required discharge limits. In most cases the final effluent BOD5 concentration is 〈10 mg l−1. The relationship between vegetated bed BOD5 inflow loadings (L 0) and outflow loadings (L) is very strong (r=0.92). Constructed wetlands with subsurface horizontal flow usually do not remove larger amounts of nitrogen and phosphorus. The results from five Czech constructed wetlands show that nitrogen removal varies among systems, but the amount of removed nitrogen is very predictable. A regression equation between nitrogen inflow loading (L 0) and outflow loading (L) produces a strong correlation (r=0.98). The most important process responsible for phosphorus removal in wetlands is precipitation with soil Ca, Fe and Al. However, the subsurface horizontal flow constructed wetlands use mostly coarse gravel and/or sandy materials and this provides little or no P precipitation. Results from monitored systems in the Czech Republic show that the percentage phosphorus removal varies widely among systems and is lower than the percentage removal of organics and suspended solids.
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  • 73
    ISSN: 1572-9834
    Keywords: Alnus glutinosa ; constructed ecosystems ; disinfection ; Iris pseudacorus ; multi-stage systems ; nitrogen ; phosphorus ; constructed treatment wetlands ; optimization ; purification efficiencies ; urban wastewaters treatment ; Typha latifolia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Tests were carried out under controlled conditions in the Experimental Plant of Viville (Arlon, Belgium) to enhance the purification of urban wastewater by “natural” means. The results demonstrate the need to structure treatment systems in a series of different artificial ecosystems (or a Hierarchical Mosaic of Artificial Ecosystems — MHEA in French). The first two levels we used were made up of an unplanted aquatic ecosystem (stabilization pond) followed by a semi-aquatic ecosystem planted withTypha latifolia L. in which the water flows over the substrate. At a flow rate of 4 m2/PE (1 PE=150 1/day of typical urban wastewaters in Belgian rural zones), this first stage substantially reduces suspended solids (SS), COD and BOD5, a significant amount of tot-N and tot-P, and reduces pathogens by 100-fold. Further, the system is easy to manage (sludge is eliminated in the first stage and biomass is collected in the second stage) and the treatment system does not clog up. Nevertheless, real and sustainable environmental protection demands even higher performance rates, and these first two stages, both in terms of design and dimension, can only be considered as a satisfactory part of a MHEA system. Artificial aquatic, semi-aquatic, and terrestrial ecosystems were systematically compared at the third and fourth stage of the system to increase the overall removal efficiency. The most complete and efficient system in our tests (i.e., the one that provides the most successful primary (SS), secondary (COD and BOD5) and tertiary (N and P) treatment and the best pathogens removal rates) was made up of 3 sequential series of ecosystems: an aquatic ecosystem whose flow went into a plantedTypha latifolia system (surface water flow), that flowed into a terrestrial ecosystem planted withAlnus glutinosa (L.) Gaertn (vertical subsurface water flow). A total surface area (stages 1–4) of 8 m2/PE ensured a high performance level whose outflow conformed to the strictest European norms.
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  • 74
    ISSN: 1573-904X
    Keywords: hIGF-I ; oxidation ; methionine ; HPLC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aim of this work was to study the kinetics of oxidation of methionine in human Insulin-like Growth Factor I (hIGF-I)1 in aqueous solution and in the solid state by the aid of quantification of oxygen. Methods. The oxidized form of hIGF-I was characterized by tryptic peptide analysis, RP-HPLC and FAB-MS and quantified by RP-HPLC. The oxygen content was quantified polarographically by a Clark-type electrode. Results. Second-order kinetics with respect to amount of protein and dissolved oxygen was found to be appropriate for the oxidation of methionine in hIGF-I. The rate constants ranged from 1 to 280 M−1 month−l and had an activation energy of 95 (+/−4) kJ/mole. Light exposure, storage temperature and oxygen content were found to have a considerable impact on the oxidation rates. No significant difference in reaction rates was found for the oxidation of hIGF-I in aqueous solution or in the solid state. A method for decreasing the oxygen content in aqueous solution without purging is described. Conclusions. Polarographic quantification of dissolved oxygen makes it possible to establish the kinetics for oxidation of proteins. The oxidation of methionine in hIGF-I appears to follow second-order kinetics.
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  • 75
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    Plant and soil 179 (1996), S. 45-56 
    ISSN: 1573-5036
    Keywords: Eucalyptus regnans ; nitrogen ; phosphorus ; soil desiccation ; soil microfractures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The poor growth of young Eucalyptus regnans seedlings in undried soil from the mature forest of E. regnans can be overcome by previously air-drying the soil or by adding sufficient amounts of complete soluble fertilizer or equivalent concentrations of P (as NaH2PO4) and N (as NaNO3). A factorial pot experiment in which phosphate and nitrate were added to undried soil indicated that P was the primary deficiency for young seedlings and that response to N did not occur until this lack was satisfied. In dried soil, seedlings also responded to additions of complete fertilizer but most of this effect was due to N rather than P. Field trials in the mature forest also indicated greater growth in dried soil than undried soil and confirmed a response of young seedlings to superphosphate. In pot experiments, the concentration of P and N per g plant dry weight after four months was relatively constant irrespective of the final size of the plant. Seedlings in dried soil extracted up to 15 times more P than did those grown in undried soil. In general, chemical analysis of soil indicated more extractable P and N from dried soil although this was not always consistently so. Soil desiccation resulted in an increase in soil surface area due to the fragmentation of larger peds and to an increase in the number of microfractures which remained in the soil crumbs after rewetting. Mycorrhiza are likely to be important since the differentiation of the growth response of seedlings in dried and undried soil, which occurred at 5–6 weeks, corresponded with the establishment of full ectomycorrhizal development (80% root tips). The factors concerned with the increase in fertility after air-drying are discussed.
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  • 76
    ISSN: 1573-5036
    Keywords: arbuscular mycorrhiza ; Glomus intraradices ; lime ; Oxisol ; phosphorus ; Ultisol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effects of liming and inoculation with the arbuscular mycorrhizal fungus, Glomus intraradices Schenck and Smith on the uptake of phosphate (P) by maize (Zea mays L.) and soybean (Glycine max [L.] Merr.) and on depletion of inorganic phosphate fractions in rhizosphere soil (Al-P, Fe-P, and Ca-P) were studied in flat plastic containers using two acid soils, an Oxisol and an Ultisol, from Indonesia. The bulk soil pH was adjusted in both soils to 4.7, 5.6, and 6.4 by liming with different amounts of CaCO3. In both soils, liming increased shoot dry weight, total root length, and mycorrhizal colonization of roots in the two plant species. Mycorrhizal inoculation significantly increased root dry weight in some cases, but much more markedly increased shoot dry weight and P concentration in shoot and roots, and also the calculated P uptake per unit root length. In the rhizosphere soil of mycorrhizal and non-mycorrhizal plants, the depletion of Al-P, Fe-P, and Ca-P depended in some cases on the soil pH. At all pH levels, the extent of P depletion in the rhizosphere soil was greater in mycorrhizal than in non-mycorrhizal plants. Despite these quantitative differences in exploitation of soil P, mycorrhizal roots used the same inorganic P sources as non-mycorrhizal roots. These results do not suggest that mycorrhizal roots have specific properties for P solubilization. Rather, the efficient P uptake from soil solution by the roots determines the effectiveness of the use of the different soil P sources. The results indicate also that both liming and mycorrhizal colonization are important for enhancing P uptake and plant growth in tropical acid soils.
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  • 77
    ISSN: 1573-5036
    Keywords: copper ; Cymbopogon winterianus ; phosphorus ; potassium ; soil bulk density ; VA mycorrhizal fungi ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Nutrient acquisition and growth of citronella Java (Cymbopogon winterianus Jowitt) was studied in a P-deficient sandy soil to determine the effects of mycorrhizal symbiosis and soil compaction. A pasteurized sandy loam soil was inoculated either with rhizosphere microorganisms excluding VAM fungi (non-mycorrhizal) or with the VAM fungus, Glomus intraradices Schenck and Smith (mycorrhizal) and supplied with 0, 50 or 100 mg P kg-1 soil. The soil was compacted to a bulk density of 1.2 and 1.4 Mg m-3 (dry soil basis). G. intraradices substantially increased root and shoot biomass, root length, nutrient (P, Zn and Cu) uptake per unit root length and nutrient concentrations in the plant, compared to inoculation with rhizosphere microorganisms when the soil was at the low bulk density and not amended with P. Little or no plant response to the VAM fungus was observed when the soil was supplied with 50 or 100 mg P kg-1 soil and/or compacted to the highest bulk density. At higher soil compaction and P supply the VAM fungus significantly reduced root length. Non-mycorrhizal plants at higher soil compaction produced relatively thinner roots and had higher concentrations and uptake of P, Zn and Cu than at lower soil compaction, particularly under conditions of P deficiency. The quality of citronella Java oil measured in terms citronellal and d-citronellol concentration did not vary appreciably due to various soil treatments.
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  • 78
    ISSN: 1573-5036
    Keywords: arbuscular mycorrhiza ; cotton ; manganese ; pH ; phosphorus ; root browning ; soil texture ; Thielaviopsis basicola ; Verticillium dahliae ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The symptoms of a growth disorder of cotton and associated properties of the soil were quantified. Data were collected from 35 sites across two irrigated fields that showed gradients in the severity of early season stunting of cotton. Ordination analysis of soil characteristics distinguished three groups of sites (A, B, and C) which corresponded to patterns of yield and early season growth. Group A and B soils had lower pH, finer texture and higher P, Zn, Mn and exchangeable Mg, K and Na than group C soils. Early season growth and arbuscular mycorrhizal colonisation of cotton at group A and B sites was much slower than at group C sites. Group B sites showed a recovery of yield later in the season while group A sites did not. Nutrient deficiencies, waterlogging, soil compaction, soil sodicity and Mn toxicity were unlikely causes of early season stunting, although soil Mn was a good predictor for the disorder. Thielaviopsis basicola, Verticillium dahliae and unidentified Chytridiomycetes were not associated with stunting and reduced yield, although other fungal pathogens may have been present. Root browning was a symptom of the disorder and suggests that pathogens, perhaps bacteria, play a causal role. This study showed that the growth disorder involved an interaction between cotton and the soil flora which was associated with heavy soil texture.
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  • 79
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    Plant and soil 184 (1996), S. 23-31 
    ISSN: 1573-5036
    Keywords: budget ; movement ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Agronomic studies on soil phosphorus dynamics have primarily focused on the plant-available inorganic P pool. However organic P and less labile inorganic pools can contribute significantly to plant P uptake. The objectives of this study were to determine the changes in inorganic and organic P pools of varying lability in and below the plowlayer after 13 years of continuous cultivation and fertilization on a Typic Paleudult in Yurimaguas, Peru. The field experiment was established after slash and burn of a secondary forest and included non-fertilized and fertilized treatments. The yearly cropping pattern consisted of an upland rice (Oryza sativa),-corn (Zea mays),-soybean (Glycine max) rotation. A modified version of the Hedley et al. procedure was used to sequentially fractionate soil P into increasingly recalcitrant organic and inorganic pools. Plowlayer accumulation of the fertilizer P occurred in all P pools. The greatest increase was in the NaOH extractable inorganic P pool. In the non-fertilized plots, the organic P decreased by 42%. Phosphorus fertilization resulted in significant movement of P below plowlayer. The accumulation occurred mostly in inorganic and organic P pools that are not quantified by traditional soil-P test methods. In fertilized plots sub-plowlayer total P increased by 90 μg g−1 (87%) while resin extractable P increased only 4 μg g−1. Phosphorus content of the organic P pools below the plowlayer increased by 24 μg g−1 (50%) in fertilized plots. The inclusion of less labile P pools in studies of P movement and the evaluation of P fertilizer residual values could lead to a better understanding of P dynamics and hence better management of P fertilization.
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  • 80
    ISSN: 1573-5036
    Keywords: pearl millet ; Pennisetum glaucum (L.) R. Br. ; phosphorus ; photosynthesis ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract There have been no studies of the effects of soil P deficiency on pearl millet (Pennisetum glaucum (L.) R. Br.) photosynthesis, despite the fact that P deficiency is the major constraint to pearl millet production in most regions of West Africa. Because current photosynthesis-based crop simulation models do not explicitly take into account P deficiency effects on leaf photosynthesis, they cannot predict millet growth without extensive calibration. We studied the effects of soil addition on leaf P content, photosynthetic rate (A), and whole-plant dry matter production (DM) of non-water-stressed, 28 d pearl millet plants grown in pots containing 6.00 kg of a P-deficient soil. As soil P addition increased from 0 to 155.2 mg P kg−1 soil, leaf P content increased from 0.65 to 7.0 g kg−1. Both A and DM had maximal values near 51.7 mg P kg−1 soil, which corresponded to a leaf P content of 3.2 g kg−1. Within this range of soil P addition, the slope of A plotted against stomatal conductance (gs) tripled, and mean leaf internal CO2 concentration ([CO2]i) decreased from 260 to 92 μL L−1, thus indicating that P deficiency limited A through metabolic dysfunction rather than stomatal regulation. Light response curves of A, which changed markedly with P leaf content, were modelled as a single substrate, Michaelis-Menten reaction, using quantum flux as the substrate for each level of soil P addition. An Eadie-Hofstee plot of light response data revealed that both KM, which is mathematically equivalent to quantum efficiency, and Vmax, which is the light-saturated rate of photosynthesis, increased sharply from leaf P contents of 0.6 to 3 g kg−1, with peak values between 4 and 5 g P kg−1. Polynomial equations relating KM and Vmax, to leaf P content offered a simple and attractive way of modelling photosynthetic light response for plants of different P status, but this approach is somewhat complicated by the decrease of leaf P content with ontogeny.
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  • 81
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    Plant and soil 181 (1996), S. 169-173 
    ISSN: 1573-5036
    Keywords: kinetics ; microbial biomass ; model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Many models that describe the turnover of the microbial biomass in soil use either first order kinetics where the rate of turnover is directly proportional to the microbial mass, or a variant of the Michaelis-Menten law that describes enzyme kinetics. To account for the different rates of microbial turnover observed at different times after the addition of substrate, some authors have suggested the existence of more than one pool of biomass. Each pool obeys the same kinetic law but with a different rate. In other experiments a disproportionately large increase in the turnover of native organisms has been observed relative to the amount of fresh substrate added. A change in the kinetic law describing the turnover of organisms can account for these observations and yet retain the simplicity of a single pool of micro-organisms. However where multiple pools of organisms are justified a mixed kinetic law with both first and second order terms may be more appropriate; in other words one pool of micro-organisms but two rate constants. The advantage of retaining a single pool of microbial biomass is that models may more readily be constructed in relation to the routine measurements of total microbial mass.
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  • 82
    ISSN: 1573-5036
    Keywords: Barro Colorado Island ; base cations ; nitrogen ; phosphorus ; seasonal variation ; semideciduous forest ; soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of seasonal water availability on soil nutrients and soil N transformations was investigated by irrigating two large plots of mature tropical forest on Barro Colorado Island (BCI), Panama, during the dry season for five consecutive years. Methods included (i) nutrient accumulation by ion-exchange resins placed on the surface of the mineral soil for contiguous 21-day periods, (ii) monthly mineral soil (0–10 cm) extractions and incubations for inorganic N and P concentrations, and (iii) leaching loss of nutrients from leaf litter samples. Rates of nutrient accumulation by the resins showed a great deal of variation between sampling dates and among years in control plots; albeit, seasonal patterns were slight, except for the highest Ca values near the end of the wet season and inorganic P (Pi) and SO4 values that peaked during the dry season. Irrigation had remarkably little effect on nutrient accumulation rates by resins, except for an increase in Mg and Na values, but did affect the timing in the temporal variation in K, Na, Ni and Pi values. In contrast, inorganic N (Ni) and Pi pools and N transformation rates in the mineral soil hardly varied among sampling dates and did not show any response to irrigation. We hypothesize that the timing of leaf litterfall and nutrient leaching from forest floor litter can set up temporal patterns in the levels of soil nutrient at the surface of the mineral soil, but the temporal patterns essentially disappear with depth in the mineral soil.
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  • 83
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    Plant and soil 186 (1996), S. 197-204 
    ISSN: 1573-5036
    Keywords: cell-wall ; groundnut ; P acquisition ; P solubilization ; phosphorus ; sorghum ; soybean ; strengite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Groundnut showed a superior ability to take up P from a soil with low P fertility compared with sorghum and soybean. This ability was not related to its better root development or production of root exudates capable of solubilizing iron-and aluminum-bound P. In efforts to determine the role of roots per se, we found that root cell walls from groundnut showed a higher P-solubilizing activity than those from soybean or sorghum. This finding corresponds well with observations in field and pot experiments using a soil with low P availability. The reaction site of P-solubilizing activity is stable against heating and enzyme digestion by cellulase and pectinase. This is probably the first evidence to demonstrate that cell walls of plant roots are involved in P-solubilizing activity. ei]Section editor: H Marschner (deceased 21 September 1996)
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  • 84
    ISSN: 1573-5117
    Keywords: sediment ; phosphorus ; silicon ; microbial activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The chemical and microbiological responses of profundal surface sediment were monitored in sediment enriched with natural settled material collected in May, July or August, and with diatom or cyanobacteria cultures. The activation of the sediment microbial community was clearest after the addition of settled seston collected in May which was richer in organic matter than those collected later in the summer. N was released when the sediment was enriched with settled seston which had been collected in July and August and had C:N ratios lower than 10:1. The diatom-rich May-material enhanced the release of P to the interstitial water, obviously because of chemical competition between P and diatom-derived Si at the sediment surface. The July- and August-materials did not release P, nor did the diatom and cyanobacteria cultures. The results thus indicate that the seasonal variations in the quality and quantity of the settling phytoplankton affect the P dynamics at the sediment surface, both chemically and biologically.
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  • 85
    ISSN: 1573-5117
    Keywords: nitrate ; phosphorus ; nutrients ; calcium ; potassium ; spiralling ; disturbance ; mediterranean ; temporary ; stream
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Uptake rate of calcium, potassium, nitrate-N and phosphorus were measured in a second order Mediterranean temporary stream, in February and March 1992. This study analyzed a period of continuous surface flow between two hydrologic disturbance events (flood and drought) of an annual hydrological cycle (1991–92). The lowest values of uptake length were recorded for nitrate-N in February 92 and calcium in March 92. Nitrate had the highest uptake rate in both release performances, and potassium showed the lowest uptake rate values. The increase of calcium and nitrate uptake rate between February 92 and March 92 suggested a higher ecosystem efficiency in nutrient retention with a higher temperature and light intensity and slower water velocity, discharge and water depth. These results obtained were similar to those reported in permanent streams, indicating that in periods of continuous surface flow (without extreme hydrologic disturbance), abiotic factors can influence nutrient retention in temporary streams.
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  • 86
    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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  • 87
    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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    Biogeochemistry 35 (1996), S. 419-432 
    ISSN: 1573-515X
    Keywords: phosphorus ; sequential extraction ; soils ; riparian forest ; seasonal pattern
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract This study addresses the temporal distribution of forms of phosphorus in the soil of a temporarily flooded riparian forest of the valley of the river Garonne (Southwest of France). A sequential extraction for forms of phosphorus of increasing chemical stability was used. During the study period (13 months), the forest was flooded a few days during March and May. In winter, resin-Pi concentration was high (26 μg g−1) in comparison to spring values (〈9 μg g−1). NaHCO3-Po, NaHCO3-Pi or NaOH-Pi concentrations increased during winter (up to 74, 124 and 78 μg g−1 respectively) and decreased significantly during spring (32, 44 and 32 μg g−1 respectively). This pattern was attributed to simultaneous mineralization and plant uptake during the growing season and to the flood events (erosional processes and P-release). During summer and fall, resin-Pi concentration increased significantly (up to 26 μg g−1 in October). NaHCO3-Po concentrations remained low during spring and summer (〈33 μg g−1), and increased significantly in fall (〉45 μg g−1 NaHCO3-Pi or NaOH-Pi increased in late spring or summer (90 μg g−1 and 68 μg g−1 respectively). Increasing concentrations of the labile forms during late spring or summer were ascribed to the warm temperature and soil dryness that limited plant growth. HCl-Pi increased regularly after the floods (174 μg g−1 before the flood events to 254 μg g−1 after the floods). Residual P presented a similar pattern i.e. 214 μg g−1 and 279 μg g−1 respectively before and after the flood events. This pattern was attributed to a progressive incorporation of flood deposits to the soil.
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  • 89
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    Photosynthesis research 48 (1996), S. 411-417 
    ISSN: 1573-5079
    Keywords: chlorophyll a fluorescence ; kinetics ; Photosystem II ; quinone acceptors ; S-states of oxygen-evolving complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The flash-induced kinetics of various characteristics of Photosystem II (PS II) in the thylakoids of oxygenic plants are modulated by a period of two, due to the function of a two-electron gate in the electron acceptor side, and by a period of four, due to the changes in the state of the oxygen-evolving complex. In the absence of inhibitors of PS II, the assignment of measured signal to the oxygen-evolving complex or to quinone acceptor side has frequently been done on the basis of the periodicity of its flash-induced oscillations, i.e. four or two. However, in some circumstances, the period four oscillatory processes of the donor side of PS II can generate period two oscillations. It is shown here that in the Kok model of oxygen evolution (equal misses and equal double hits), the sum of the concentrations of the S 0 and S 2 states (as well as the sum of concentrations of S 1 and S 3 states) oscillates with period of two: S 0+S 2→S 1+S 3→S 0+S 2→S 1+S 3. Moreover, in the generalized Kok model (with specific miss factors and double hits for each S-state) there always exist such ε0, ε1, ε2, ε3 that the sum ε0[S0] + ε1[S1] + ε2[S2] + ε3[S3] oscillates with period of two as a function of flash number. Any other coefficients which are linearly connected with these coefficients, % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGak0dh9WrFfpC0xh9vqqj-hEeeu0xXdbba9frFj0-OqFf% ea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr% 0-vqpWqaaeaabiGaciaacaqabeaadaqaaqaaaOqaaiqbew7aLzaaja% aaaa!3917!\[\hat \varepsilon \]i = c1εi + c2, also generate binary oscillations of this sum. Therefore, the decomposition of the flash-induced oscillations of some measured parameters into binary oscillations, depending only on the acceptor side of PS II, and quaternary oscillations, depending only on the donor side of PS II, becomes practically impossible when measured with techniques (such as fluorescence of chlorophyll a, delayed fluorescence, electrochromic shift, transmembrane electrical potential, changes of pH and others) that could not spectrally distinguish the donor and acceptor sides. This property of the Kok cycle puts limits on the simultaneous analysis of the donor and acceptor sides of the RC of PS II in vivo and suggests that binary oscillations are no longer a certain indicator of the origin of a signal in the acceptor side of PS II.
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  • 90
    ISSN: 1573-0867
    Keywords: fertilizer ; nitrogen ; nutrition ; pastures ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In order to propose consistent decision rules for fertilizer supply, a study was made on the effect of additions of N and P fertilizers and of their interaction on the above-ground dry matter yield of pastures during spring. The interaction between N and P could occur through nutrient acquisition or nutrient efficiency for growth. We therefore characterised the herbage N and P status (N and P index) from previously established critical curves of herbage mineral content according to above-ground dry matter. First we studied the effect of N and P addition on herbage nutrient status. Secondly, we expressed the above-ground dry matter as a function of the herbage nutrient status. This study consisted of four treatments applied to four permanent pastures which had a low phosphorus availability. The results showed a positive effect of P supply on the herbage nitrogen status, which may be due to an increase of organic matter mineralization or root growth. The P herbage status decreased only if N was supplied without P. The dry matter yield was positively related to the herbage nitrogen status, but a low P herbage status reduced the slope of the relationship. For the pastures studied, the indirect effect of P supply on above-ground dry matter, revealed by an increase in N index, was greater than its direct effect. This methodology allows us to distinguish the direct and indirect effects of N and P addition on herbage growth at field level. It could be used to propose consistent rules to manage jointly both N and P supplies.
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  • 91
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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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  • 92
    ISSN: 1572-9680
    Keywords: Imperata cylindrica ; Mucuna pruriens ; phosphorus ; soil organic matter ; Sumatra
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Imperata cylindrica grasslands are widely believed to indicate poor soil fertility. Soil fertility improvement may have to be an important component of a reclamation strategy. Data for Sumatra, Indonesia indicate, however, that Imperata occurs on a broad range of soil types and is not confined to the poorest soils. A direct role of Imperata in soil degradation cannot be ascertained. In many instances, however, Imperata soils are low in available P and effective N supply. The use of rock phosphate in combination with erosion control (‘fertility traps’) and legume cover crops can be effective in restoring soil fertility. Case studies for a number of sites in Sumatra have confirmed the practical possibility of reclaiming grasslands for food and tree crops.
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  • 93
    ISSN: 1573-5036
    Keywords: high-affinity ; kinetics ; low-affinity ; potassium ; regulation ; transport
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Over the last five years, the cloning and characterization of K+ transport genes corresponding to K+ channels (KAT1, AKT1, KST1, AKT2), associated subunits (KAB1) and a high-affinity transporter (HKT1) has opened up important new avenues for research on plant K+ nutrition. With the abundance of molecular data now available it seems timely to link this information with the wealth of data previously accumulated on the physiology of plant K+ acquisition. The ultimate goal of all this research is to gain a better understanding of K+ transport and nutrition in the intact plant. Thus it is important to begin to integrate the molecular research with results from biochemical and physiological research conducted at the cellular, root and whole plant levels. This article will focus on describing the features of the cloned K+ transporters and their possible roles in mediating high- and low-affinity K+ uptake from the soil, as well as how K+ acquisition may be regulated.
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  • 94
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    Photosynthesis research 49 (1996), S. 37-48 
    ISSN: 1573-5079
    Keywords: cytochrome f ; kinetics ; midpoint potential ; plastocyanin ; P700 ; Rieske centre
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Effects of three inhibitors of quinol oxidation in the chloroplast cytochrome bf complex (stigmatellin, tridecylstigmatellin and dibromothymoquinone) were studied in an isolated system comprising Photosystem I (PS I) particles, plastocyanin (PC) and cytochrome bf complex, in the absence of quinol or quinone. Addition of these inhibitors increased the extent of cytochrome f oxidation after a laser flash created oxidised PS I reaction centre (P700) and PC, and decreased somewhat the extent of PC oxidation. The re-reduction of oxidised P700 was more complete than when inhibitor was absent. The data were simulated with reactions which included the putative reduction of cytochrome f by the Rieske centre (FeS) and different rate-coefficients according as to whether inhibitor was bound to the bf complex or not. It was concluded that under the conditions studied the Rieske centre donated electrons to oxidised cytochrome f and plastocyanin with an average rate coefficient of 35 s−1. This electron transfer was prevented by any of the three inhibitors, which also increased the equilibrium coefficient for the cytochrome f/PC reaction by a maximum factor of two. This increase corresponded to a decrease in the back reaction coefficient and an increase in the forward rate. The equilibrium coefficient for the reduction of oxidised P700 by PC was about 2 in the absence of inhibitor but increased to about 20 in their presence, but only if cytochrome bf complex was additionally present. This was attributed to the transient formation of complexes between P700 with bound plastocyanin, and bf complex. The operative mid-point potential of FeS, if that of cytochrome f is 370 mV, was 390 mV. Deviations in midpoint potentials (P700/plastocyanin) from solution values were attributed to the bound state of the reactants. Estimates were made of the binding coefficient of each of the three inhibitors to p-sites in the cytochrome bf complex in the absence of competing quinol. A stoichiometry of two inhibitors per bf dimer was necessary to cause the above changes in reduction potential of cyt f and PC. A result of one inhibitor per dimer was statistically unlikely, particularly in the case of tridecylstigmatellin.
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  • 95
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    Journal of aquatic ecosystem stress and recovery 5 (1996), S. 23-40 
    ISSN: 1573-5141
    Keywords: ecosystem modeling ; fishery management ; organic carbon mass balance ; stocking ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Present-day ecosystem management involves understanding of the synergistic effect of multiple stressors on multiple and frequently nebulous management end-points. An example is the simultaneous management of nutrient load reductions and salmon stocking in Lake Ontario. In this study, a simple whole-lake annual time scale model was developed to assess the relationship between these two stressors and various ecosystem responses. The model was used to explore the utility of some possible management end-points for ecosystem health. In historical simulations, production per stocked fish and salmon survival appeared to be good indicators, while nutrient recycling rate and average ecosystem-wide food limitation were found to be fairly unresponsive to the two stressors. The model was further used to predict long term averages of salmon biomass and selected health indicators at various sustained loading and stocking rates. Salmon biomass increased with stocking rate at all stocking rates examined, but the rate of increase declined somewhat at high stocking rates. The response of salmon biomass to nutrient loading appeared to be approximately sigmoidal i.e. there was a nutrient threshold below which fish biomass could not be sustained and another nutrient threshold above which salmon biomass either remained constant or even decreased. The response to either stressor was found to be modified by the value of the other stressor, illustrating the importance of ecosystem-level models for aquatic ecosystem management.
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  • 96
    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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  • 97
    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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  • 98
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    Water, air & soil pollution 90 (1996), S. 295-300 
    ISSN: 1573-2932
    Keywords: dechlorination ; coulometry ; sulfite ; water ; rate ; chloramine ; residual ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The kinetics of dechlorination show that chlorinated organic amines are not completely dechlorinated during typical contact times. Analytical techniques for measuring residual sulfite must maintain pH neutrality in order to represent the actual extent of dechlorination and must allow for rapid and convenient operation near the sampling site in order to minimize errors due to air oxidation during the procedure. A portable, analog circuitry-based instrument using constant current coulometry with amperometric end point detection was developed and evaluated. laboratory and field operation of the instrument showed an analytical range of 0.015-to-25.0 mg sulfite/l. Relative standard deviation was typically 1–2%.
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  • 99
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    Environmental monitoring and assessment 43 (1996), S. 117-124 
    ISSN: 1573-2959
    Keywords: geochemistry ; metals ; phosphorus ; fractionation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The Yamuna river is the largest tributary of the Ganges river system. It originates in the Himalayas and flows through a varied geological terrain encompassing a large basin area. Metals Fe, Mn, Pb, Zn, Cu in different chemical fractions of suspended sediments such as exchangeable, carbonates, Fe−Mn oxides, organics and residual fractions were studied. Phosphorus associated with different chemical forms are discussed. The metals are mostly associated with residual fractions in the sediments followed by organics, Fe−Mn oxides, exhangeable and carbonates. Intensive use of chemical fertilizers and pesticides in agriculture in the basin affects the high inorganic phosphorus content in sediments.
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  • 100
    ISSN: 1573-2983
    Keywords: Zinc ; copper ; manganese ; iron ; lead ; cadmium ; nickel ; phosphorus ; limestone ; fertilizer ; sewage sludge compost
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Medicine
    Notes: Abstract Previous research has demonstrated that many urban soils are enriched in Pb, Cd and Zn. Culture of vegetable crops in these soils could allow transfer of potentially toxic metals to foods. ‘Tanya’ lettuce (Lactuca sativa L.) was grown in pots of five urban garden soils and one control agricultural soil to assess the effect of urban-soil metal enrichment, and the effect of soil amendments, on heavy metal uptake by garden vegetables. The amendments included NPK fertilizer, limestone, Ca(H2PO4)2, and two rates of limed sewage sludge compost. Soil Cd ranged from 0.08 to 9.6 mg kg−1; soil Zn from 38 to 3490 mg kg−1; and soil Pb from 12 to 5210 mg kg−1. Lettuce yield on the urban garden soils was as great as or greater than that on the control soil. Lettuce Cd, Zn and Pb concentrations increased from 0.65, 23, and 2.2 mg kg−1 dry matter in the control soil to as high as 3.53, 422 and 37.0 mg kg−1 on the metal-rich urban garden soils. Adding limestone or limed sewage sludge compost raised soil pH and significantly reduced lettuce Cd and Zn, while phosphate fertilizer lowered soil pH and had little effect on Zn but increased Cd concentration in lettuce. Urban garden soils caused a significant increase in lettuce leaf Pb concentration, especially on the highest Pb soil. Adding NPK fertilizer, phosphate, or sludge compost to two high Pb soils lowered lettuce Pb concentration, but adding limestone generally did not. On normally fertilized soils, Pb uptake by lettuce was not exceptionally high until soil Pb substantially exceeded 500 mg kg−1. Comparing garden vegetables and soil as potential sources of Pb risk to children, it is clear that the risk is greater through ingestion of soil or dust than through ingestion of garden vegetables grown on the soil. Urban dwellers should obtain soil metal analyses before selecting garden locations to reduce Pb risk to their children.
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