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Measured Rate (measured + rate)
Selected AbstractsUse of caesium-137 data to evaluate SHETRAN simulated long-term erosion patterns in arable landsHYDROLOGICAL PROCESSES, Issue 10 2004Y. Norouzi Banis Abstract The caesium-137 method of quantifying soil erosion is used to provide field data for validating the capability of the SHETRAN modelling system for predicting long-term (30-year) erosion rates and their spatial variability. Simulations were carried out for two arable farm sites (area 3,5 ha) in central England for which average annual erosion rates of 6·5 and 10·4 t ha,1 year,1 had already been determined using caesium-137 measurements. These rates were compared with a range of simulated values representing the uncertainty in model output derived from uncertainty in the evaluation of model parameters. A successful validation was achieved in that the simulation range contained the measured rate at both sites, whereas the spatial variability was reproduced excellently at one site and partially at the other. The results indicate that, as the caesium-137 technique measures the erosion caused by all the processes acting at a site, it is relevant to hydrologically based models such as SHETRAN only if erosion by wind, agricultural activities and other processes not represented in the model are insignificant. The results also indicate a need to reduce the uncertainty in model parameter evaluation. More generally, the caesium-137 technique is shown to provide field data that improve the severity of the validation procedure (accounting for internal as well as outlet conditions) and that add spatial variability to magnitude as a condition for identifying unrealistic parameter sets when seeking to reduce simulation uncertainty. Copyright © 2004 John Wiley & Sons, Ltd. [source] How does photorespiration modulate leaf amino acid contents?PLANT CELL & ENVIRONMENT, Issue 7 2002A dual approach through modelling, metabolite analysis Abstract The aim of this work was to establish the quantitative impact of photorespiration on leaf amino acid contents. Attached leaves of wheat and potato were incubated for 30,40 min under defined conditions in which net CO2 uptake (A) was manipulated by irradiance, ambient CO2 or ambient O2. The incubated portion of the leaf was sampled by a rapid-quench method and photorespiratory flux (vo) was modelled from the measured rate of net CO2 uptake. In both wheat and potato, the ratio between glycine and serine showed a strong positive correlation with vo. Aspartate and alanine correlated negatively with vo but glutamate and glutamine showed less clear relationships. In potato, glutamate and glutamine did not correlate clearly with either A or vo. In wheat, glutamine showed a general increase with A but no relationship with vo, whereas 2-oxoglutarate contents correlated positively with vo and negatively with A. As a result, glutamine : glutamate and glutamine : 2-oxoglutarate increased with net CO2 uptake in wheat, observations that are attributed primarily to imperfect and variable coupling between the supply of NH3 in primary nitrogen assimilation and the associated delivery of 2-oxoglutarate to the chloroplast. A simple theoretical analysis is used to illustrate the potentially marked impact of primary nitrogen assimilation on leaf glutamine, even against a background of high rates of photorespiratory ammonia recycling. [source] The Reaction of Ozone with the Hydroxide Ion: Mechanistic Considerations Based on Thermokinetic and Quantum Chemical Calculations and the Role of HO4, in Superoxide DismutationCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2010Gábor Merényi Prof. Abstract The reaction of OH, with O3 eventually leads to the formation of . OH radicals. In the original mechanistic concept (J. Staehelin, J. Hoigné, Environ. Sci. Technol.1982, 16, 676,681), it was suggested that the first step occurred by O transfer: OH,+O3,HO2,+O2 and that . OH was generated in the subsequent reaction(s) of HO2, with O3 (the peroxone process). This mechanistic concept has now been revised on the basis of thermokinetic and quantum chemical calculations. A one-step O transfer such as that mentioned above would require the release of O2 in its excited singlet state (1O2, O2(1,g)); this state lies 95.5,kJ,mol,1 above the triplet ground state (3O2, O2(3,g,)). The low experimental rate constant of 70,M,1,s,1 is not incompatible with such a reaction. However, according to our calculations, the reaction of OH, with O3 to form an adduct (OH,+O3,HO4,; ,G=3.5,kJ,mol,1) is a much better candidate for the rate-determining step as compared with the significantly more endergonic O transfer (,G=26.7,kJ,mol,1). Hence, we favor this reaction; all the more so as numerous precedents of similar ozone adduct formation are known in the literature. Three potential decay routes of the adduct HO4, have been probed: HO4,,HO2,+1O2 is spin allowed, but markedly endergonic (,G=23.2,kJ,mol,1). HO4,,HO2,+3O2 is spin forbidden (,G=,73.3,kJ,mol,1). The decay into radicals, HO4,,HO2.+O2.,, is spin allowed and less endergonic (,G=14.8,kJ,mol,1) than HO4,,HO2,+1O2. It is thus HO4,,HO2.+O2., by which HO4, decays. It is noted that a large contribution of the reverse of this reaction, HO2.+O2.,,HO4,, followed by HO4,,HO2,+3O2, now explains why the measured rate of the bimolecular decay of HO2. and O2., into HO2,+O2 (k=1×108,M,1,s,1) is below diffusion controlled. Because k for the process HO4,,HO2.+O2., is much larger than k for the reverse of OH,+O3,HO4,, the forward reaction OH,+O3,HO4, is practically irreversible. [source] Oxidative transformation of tetrachlorophenols and trichlorophenols by manganese dioxideENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2009Ling Zhao Abstract This study examined the transformation kinetics of three tetrachlorophenols (TeCPs) and three trichlorophenols (TCPs) in the presence of MnO2 under different solution chemistry conditions. The reaction rate measured for each CP decreased as a function of solution pH, and under the same solution chemistry conditions, the measured rates may depend primarily on both the adsorbability at the MnO2 surfaces and the isomeric structures of the CPs. Isomeric effects indicated that chloro substituent on ortho or para positions exhibited faster rates of transformation than on meta positions. Gas chromatography-mass spectrometry analysis with a derivatization method showed that dimers including polychlorinated phenoxyphenols and chlorinated polyhydroxybi-phenyl were among the major products for all CPs. Monomeric products were among the major products of 2,4,6-TCP, 2,3,4-TCP, and 2,3,4,6-TeCP, whereas trimeric products also were among the major products of 2,3,4-TCP and 2,4,5-TCP. It appeared that hydroxylation of CPs and formation of dimeric or trimeric products via oxidative coupling were the major reaction mechanisms involved in the oxidation of CPs by MnO2. [source] Effect of ethoxylate number and alkyl chain length on the pathway and kinetics of linear alcohol ethoxylate biodegradation in activated sludgeENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2004Nina R. Itrich Abstract Batch activated-sludge die-away studies were conducted with various pure homologs to determine the effect of ethoxylate number and alkyl chain length on the kinetics of primary and ultimate biodegradation of linear alcohol ethoxylates. The 14C-(ethoxylate) homologs C14E1, C14E3, C14E6, and C14E9 were used to investigate the effect of ethoxylate number, and 14C-(ethoxylate) homologs C12E6, C14E6, and C16E6 were used to examine the effect of chain length. Activated sludge was dosed with a trace concentration (0.2 ,M) of each homolog, and the disappearance of parent, formation of metabolites, production of 14CO2, and uptake into solids were monitored with time. Ethoxylate number had little effect on the first-order decay rates for primary biodegradation, which ranged from 61 to 78 h,1. However, alkyl chain length had a larger effect, with the C16 chain-length homolog exhibiting a slower rate of parent decay (18 h,1) compared to its corresponding C12 and C14 homologs (61,69 h,1). Ethoxylate number affected the mechanism of biodegradation, with fission of the central ether bond to yield the corresponding fatty alcohol and (poly)ethylene glycol group increasing in dominance with increasing ethoxylate number. Based upon the measured rates of primary biodegradation, removal of parent during activated-sludge treatment was predicted to range between 99.7 and 99.8% for all homologs except C16E6, which had a predicted removal of 98.9%. Based upon the measured rates of ultimate biodegradation, removal of ethoxylate-containing metabolites was predicted to exceed 83% for all homologs. These predictions corresponded closely with previously published removal measurements in laboratory continuous activated-sludge systems and actual treatment plants. [source] | ||||||||||