Linear free energy relationships for metal-ligand complexation: Monodentate binding to negatively-charged oxygen donor atoms

The analysis presented below suggests that the following equation models monodentate binding to negatively-charged oxygen donor atoms with no distinction between phenolic, carboxylic or inorganic hydroxide functional groups: log K_ML = α_O log K_HL + β_O; where K_ML is the metal-ligand formation constant, K_HL is the corresponding proton-ligand formation constant, and α_O and β_O are termed the Irving-Rossotti slope and intercept, respectively. Linear free energy relationships (LFERs) of this type are presented for 24 different metal ions complexing to negatively-charged oxygen donor atoms. Ligands selected for use in LFERs meet the following criteria: (i) they contain negatively-charged oxygen donor atoms (e.g., carboxylic acids and phenols), (ii) they are capable of only monodentate binding to metal ions, (iii) steric hindrances are not expected to influence the extent of metal-ligand binding, and (iv) the negatively-charged oxygen donor atom is the only functional group that imparts charge. The intercept of all LFERs was nearly zero for all metal ions investigated (β_O ≈ 0). The magnitude of α_O indicates the relative preference of metal binding to negatively-charged oxygen donor atoms and to the proton. Values of α_O can be used in QSARs (quantitative structure activity relationships) to estimate metal-NOM (natural organic matter) binding constants employed in the Windermere Humic Aqueous Model (WHAM) version V.     

A statistical–dynamical method for predicting estuary morphology

A statistical–dynamical model for estuary morphodynamics is presented and demonstrated with a case study on the Humber Estuary, UK. The model presented here is hybrid in nature where simplified process dynamics are combined with a data-driven approach. The modelling methodology uses an inverse technique to construct an unknown source function in the model-governing equation, using historic measurements of estuary bathymetry. Spatial and temporal variability of the source function was established using empirical orthogonal eigenfunction analysis. Predictions of estuary morphology are obtained by extrapolating the temporal coefficients of the EOFs, in order to construct a predicted source function which is then used in the hybrid morphodynamic equation to obtain the predicted estuary morphology. The model was applied to predict the morphological evolution of the Humber Estuary over a period of a decade. Predicted results were compared with measured bathymetry data. The results reveal that the model captured the decadal scale morphodynamic response of the estuary with a good qualitative accuracy, despite the simplified approach used in the model. The accuracy of model predictions can be greatly improved if high-frequency bathymetry data are available.     

Long-term morphodynamic evolution of estuaries: An inverse problem

A new technique for predicting long-term variations in estuary morphology is developed using a morphological evolution equation that isolates diffusive and non-diffusive processes in estuaries. The contribution from non-diffusive processes to the morphological changes of the estuary is incorporated in the governing equation by a source function. The source function is derived by solving an inverse problem using historic survey data of the Humber estuary, UK covering a period of 150 years.     

Fractal interrelationships between topography and structure

Factal interrelationships between topography and structure are investigated in two areas of the North American central Appalachian Mountains: one in the intensely deformed Valley and Ridge province and the other in the relatively undeformed foreland area of the Appalachian Plateau province. In the Valley and Ridge province the fractal dimensions of topographic and structural relief vary systematically along the strike of major folds following a second-order polynominal trend. Cross-correlation of the fractal dimensions of topography to structure indicates that there is a significant positive correlation between the two. Fractal analysis of topography in the relatively undeformed foreland area of the Appalachian Plateau revealed no significant variation in the fractal characteristics of topography across the study area, consistent with the lack of near-surface structure. However, fractal analysis of deeper structures beneath the Plateau area undertaken using reflection seismic data revealed step-wise increases in fractal dimension from the deeply buried Precambrian basement to the near-surface. These vertical changes in fractal dimension can be related to the tectonic history of the area. Taken together, these studies indicate that fractal analysis provides a means to quantify and compare the influence of near-surface structure on topographic development and lateral and vertical structural variability. Fractal analysis provides a means to characterize the systematic changes in the complex patterns formed by topography and structure and the interrelationships between them. Similarity in their fractal characteristics implies similarity in the relative amplitude and abundance of different wavelength features in the topographic or structural profile. © 1998 John Wiley & Sons, Ltd.     

An investigation of the multi-scale temporal variability of beach profiles at Duck using wavelet packet transforms

In an earlier paper a particular discrete wavelet transform (DWT) was used to study the complex variation of beach profile changes. However, use of the DWT requires that the sequence of spatial and temporal resolution is fixed as a dyadic sequence, which means that the variability over longer intervals is not characterised well. Here we introduce the discrete wavelet packet transform (DWPT) that uses an adaptive scaling to partition the data variance, according to an entropy cost function. The advantages of this approach are demonstrated by its application to the study of temporal variability of a 22 year record of beach profile data from the Field Research Facility (FRF) at Duck, North Carolina, USA. Time series of beach elevations at three locations across a particular profile are investigated in detail. We conclude that the DWPT provides a superior analysis of non-stationary time series to that of the DWT, with improved resolution of the scale intervals of the variability. The beach elevation around the shoreline is shown to respond at both sub-annual and interannual scales, but variability at an annual scale is weak. Moving seaward into deeper water, the variance is partitioned into fewer and longer scales. It is confirmed that elevation changes around the inner bar at Duck exhibit a strong interannual variation consistent with Plant et al. (Plant, N.G., Holman, R.A. and Freilich, M.H., 1999. A simple model for interannual sandbar behaviour. Journal of Geophysical Research 104(C7), 15755–15776). Around 23% of the variance around the inner bar is explained at the temporal scale of 64–128 months, which is consistent with the bar behaviour of 6 years found by Ruessink et al. (Ruessink, B. G., Wijnberg, K. M., Holman, R. A., Kuriyama, Y. and Van Enckevort, I. M. J., 2003. Intersite comparison of interannual nearshore bar behaviour. Journal of Geophysical Research, 108 (C8): 1–12). A significant new finding is, however, that about 26% of the variance is attributable to temporal scales of 16–21.3 months. Reconstruction of the wavelet packet components for individual temporal scales is shown to provide a means for identifying the impact and scale of non-stationary events, such as storms, on the beach response. This provides further information that can be used to interpret the morphological changes in terms of the forcing processes and also serves to inform morphodynamic modelling.     

The Neupert effect: What can it tell us about the impulsive and gradual phases of solar flares?

The Neupert effect is the name given to the correlation observed in many flares between the time-integrated microwave and hard X-ray emissions and the soft X-ray emission light curve. We have used hard X-ray data from the Hard X-Ray Burst Spectrometer (HXRBS) on the Solar Maximum Mission (SMM) and soft X-ray data from the detector on GOES to determine what fraction of all events show this correlation and how the correlation changes from the impulsive to the gradual phase. We have found that of 66 HXRBS events observed in 1980 with a peak rate of > 1000 counts s^-1, 58 (80%) showed good correlations with peaks in the GOES time derivative plot corresponding to peaks in the hard X-ray (HXR) plots to within ±20 s. In 20 of these good-correlation cases (30%), the soft X-ray (SXR) time derivative stays high after the HXR emission has decreased suggesting that the later emissions result from energy release in a loop already affected by the initial energy release. In 8 of the 13 flares that showed poor correlation, the SXR time derivative shows no peak corresponding to the initial HXR impulsive peak that has structure on a time scale of 1 s. This suggests that in these events the initial impulsive energy release results primarily in electron acceleration, and that the secondary plasma heating from the accelerated electrons contributes relatively little compared to the more gradual plasma heating already taking place at the same time. The more gradually varying events, commonly referred to as type C flares, tend to show poorer correlation between the SXR time derivative and the HXR time profile. Of 26 GOES X1 or greater flares recorded between 1980 and 1989 with HXR peaks lasting over 10 rain, 13 (50%) showed poor correlation with the gradual HXR peaks either not registering at all in the SXR time derivative plots or showing up as very broad peaks. In one case, on 1981 April 26, the SXR time derivative peak was delayed by 13 rain. Only 17 (65%) of the 26 X-flares had an earlier, impulsive component and of those, 12 (71%) showed good correlation between the impulsive peaks.     

Origin and significance of 13-hydroxychlorophyll derivatives in sediments

The authenticity of hydroxychlorophyll derivatives in sediments has been verified by subjecting pure chlorophyll preparations to the extraction method used for sediments. Model studies of chlorophyll autoxidation reveal hydroxychlorophyll as the major product formed in the presence of hydrogen peroxide. Its stability to further oxidation implies that hydroxychlorophyll derivatives are not precursors of aetioporphyrins and are more likely to produce cycloalkanoporphyrins via the processes of diagenesis. The occurrence of 13²-hydroxyphaeophytin a throughout a sediment core from Loch Ness confirms it to be a widespread chlorophyll oxidation product formed during early diagenesis. Profiles of hydroxychlorophyll derivatives in a sediment core from an Antarctic lake demonstrate their potential for use as markers of oxidation processes in palaeoenvironmental assessment.