Relation between effective atomic charge and chemical shifts in X-ray absorption spectra of transition-metal compounds

Chemical shifts of K absorption discontinuities, Delta E, of several manganese, iron and cobalt oxides with the metal in the formal oxidation states between +2 and +4, have been measured. These data, together with data in the literature on other compounds of these metals, can be fitted into the expression Delta E=aq+bq2, where q is the effective atomic charge on the metal. Theoretical considerations also support this functional relationship between Delta E and q.

29Si NMR chemical shifts in silicates

29Si chemical shifts in a wide variety of silicates in crystalline, glassy and gel states have been related to a parameter, P, which takes into account the electronegativity and the structural description of the silicate units as well as the ionic potential of the modifier cation. The relation, δ(ppm)=28.4 [1−exp(−P)]−110.5, besides having predictive value, satisfactorily accounts for all the available chemical-shifts data on silicates and shows the right kind of limiting behaviour, with δ approaching the Q0 value at large P.

Leaf flushing phenology and herbivory in a tropical dry deciduous forest, southern India

Patterns of leaf-flushing phenology of trees in relation to insect herbivore damage were studied at two sites in a seasonal tropical dry forest in Mudumalai, southern India, from April 1988 to August 1990. At both sites the trees began to flush leaves during the dry season, reaching a peak leaf-flushing phase before the onset of rains. Herbivorous insects emerged with the rains and attained a peak biomass during the wet months. Trees that flushed leaves later in the season suffered significantly higher damage by insects compared to those that flushed early or in synchrony during the peak flushing phase. Species whose leaves were endowed with physical defenses such as waxes suffered less damage than those not possessing such defenses. There was a positive association between the abundance of a species and leaf damage levels. These observations indicate that herbivory may have played a major role in moulding leaf flushing phenology in trees of the seasonal tropics.

Reproductive phenology of a tropical dry forest in Mudumalai, Southern India

1 Flowering and fruiting phenologies of a tropical dry forest in Mudumalai, southern India, were studied between April 1988 and August 1990. Two sites, a wetter site I receiving 1100mm and a drier site II receiving 600mm of rainfall annually, are compared. A total of 286 trees from 38 species at site I and 167 trees from 27 species at site II was marked for phenological observations. There were 11 species common to the two sites. Several hypotheses relating to the evolution of reproductive phenology are tested. 2 Frequency of species flowering attained a peak at site I during the dry season but at site II, where soil moisture may be limiting during the dry months, the peak was during the wet season. At both sites a majority of species flushed leaves and flowered simultaneously. Among various guilds, the bird-pollinated guild showed distinct dry season flowering, which may be related to better advertisement of large flowers to pollinators during the leafless dry phase. The wind-pollinated guild flowered mainly during the wet season, when wind speeds are highest and favourable for pollen transport. The insect-pollinated guild showed no seasonality in flowering in site I but a wet season flowering in site II. 3 Fruiting frequency attained a peak in site I during the late wet season extending into the early dry season; a time-lag correlation showed that fruiting followed rainfall with a lag of about two months. Site II showed a similar fruiting pattern but this was not statistically significant. The dispersal guilds (animal, wind, and explosive passively-dispersed) did not show any clear seasonality in fruiting, except for the animal-dispersed guild which showed wet season fruiting in site I. 4 Hurlbert's overlap index was also calculated in order to look at synchrony in flowering and fruiting irrespective of climatic (dry and wet month) seasonality. In general, overlap in flowering and fruiting guilds was high because of seasonal aggregation. Among the exceptions, at site II the wind-pollinated flowering guild did not show significant overlap between species although flowering aggregated in the wet season. This could be due to the need to avoid heterospecific pollen transfer. 5 Rarer species tended to flower earlier in the dry season and this again could be an adaptation to avoid the risk of heterospecific pollen transfer or competition for pollinators. The more abundant species flowered mainly during the wet season. Species which flower earlier have larger flowers and, having invested more energy in flowers, also have shorter flower to fruit durations.

Phenology of tree species of tropical moist forest of Uttara Kannada district, Karnataka, India

Phenological observations on tree species in tropical moist forest of Uttara Kannada district (13ℴ55′ to 15ℴ31′ N lat; 74ℴ9′ to 75ℴ10′ E long) during the years 1983–1985 revealed that there exists a strong seasonality for leaf flush, leaf drop and reproduction. Young leaves were produced in the pre-monsoon dry period with a peak in February, followed by the expansion of leaves which was completed in March. Abscission of leaves occurred in the post-monsoon winter period with a peak in December. There were two peaks for flowering (December and March), while fruit ripening had a single peak in May–June, preceding the monsoon rainfall. The duration of maturation of leaves was the shortest, while that of full ripening of fruits was the longest. Mature flowers of evergreen species lasted longer than those of deciduous species; in contrast the phenophase of ripe fruits of deciduous species was longer than that of evergreen species.

Data rectification and detection of trend shifts in jet engine path measurements using median filters and fuzzy logic

Filtering methods are explored for removing noise from data while preserving sharp edges that many indicate a trend shift in gas turbine measurements. Linear filters are found to be have problems with removing noise while preserving features in the signal. The nonlinear hybrid median filter is found to accurately reproduce the root signal from noisy data. Simulated faulty data and fault-free gas path measurement data are passed through median filters and health residuals for the data set are created. The health residual is a scalar norm of the gas path measurement deltas and is used to partition the faulty engine from the healthy engine using fuzzy sets. The fuzzy detection system is developed and tested with noisy data and with filtered data. It is found from tests with simulated fault-free and faulty data that fuzzy trend shift detection based on filtered data is very accurate with no false alarms and negligible missed alarms.

Vegetative phenology of tropical montane forests in the Nilgiris, South India

Spatial and temporal variation in foliar phenology plays a significant role in growth and reproduction of a plant species. Foliar phenology is strongly influenced by environmental factors such as rainfall. A study on phenology of tropical montane forests was undertaken in three different forest patches of the Nilgiri Mountains in peninsular India above 2000 meters ASL. Since August 2000, 500 trees belonging to 70 species of angiosperms were monitored for both vegetative and reproductive phenologies on a monthly basis. Climate data were collected from nearby weather stations. This paper reports results of the study from August 2000 - August 2003 on foliar phenology. Non-parametric correlations and multiple regressions were performed to analyse the influence of environmental factors such as rainfall, temperature and sunshine on foliar phenology. It was found that moisture related factors had a negative influence on the leaf initiation. Circular statistical analyses were performed to understand the seasonality in different phenophases of foliar phenology. Different phenophases of leafing were not significantly seasonal. Results are discussed and compared among three different forest patches on the Nilgiri plateau and also with other montane forest patches across the globe.

Robustness of early warning signals of regime shifts in time-delayed ecological models

Various ecological and other complex dynamical systems may exhibit abrupt regime shifts or critical transitions, wherein they reorganize from one stable state to another over relatively short time scales. Because of potential losses to ecosystem services, forecasting such unexpected shifts would be valuable. Using mathematical models of regime shifts, ecologists have proposed various early warning signals of imminent shifts. However, their generality and applicability to real ecosystems remain unclear because these mathematical models are considered too simplistic. Here, we investigate the robustness of recently proposed early warning signals of regime shifts in two well-studied ecological models, but with the inclusion of time-delayed processes. We find that the average variance may either increase or decrease prior to a regime shift and, thus, may not be a robust leading indicator in time-delayed ecological systems. In contrast, changing average skewness, increasing autocorrelation at short time lags, and reddening power spectra of time series of the ecological state variable all show trends consistent with those of models with no time delays. Our results provide insights into the robustness of early warning signals of regime shifts in a broader class of ecological systems.

Ab Initio MD Simulations of the Bronsted Acidity of Glutathione in Aqueous Solutions: Predicting pK(a) Shifts of the Cysteine Residue

The tripeptide glutathione (GSH) is one of the most abundant peptides and the major repository for nonprotein sulfur in both animal and plant cells. It plays a critical role in intracellular oxidative stress management by the reversible formation of glutathione disulfide with the thiol-disulfide pair acting as a redox buffer. The state of charge of the ionizable groups of GSH can influence the redox couple, and hence the pK(a) value of the cysteine residue of GSH is critical to its functioning. Here we report ab initio Car-Parrinello molecular dynamics simulations of glutathione solvated by 200 water molecules, all of which are considered in the simulation. We show that the free-energy landscape for the protonation-deprotonation reaction of the cysteine residue of GSH computed using metadynamics sampling provides shift in the dissociation constant values as compared with the isolated accurate estimates of the pK(a) and correctly predicts the cysteine amino acid.

Chemical Shifts to Metabolic Pathways: Identifying Metabolic Pathways Directly from a Single 2D NMR Spectrum

Identifying cellular processes in terms of metabolic pathways is one of the avowed goals of metabolomics studies. Currently, this is done after relevant metabolites are identified to allow their mapping onto specific pathways. This task is daunting due to the complex nature of cellular processes and the difficulty in establishing the identity of individual metabolites. We propose here a new method: ChemSMP (Chemical Shifts to Metabolic Pathways), which facilitates rapid analysis by identifying the active metabolic pathways directly from chemical shifts obtained from a single two-dimensional (2D) C-13-H-1] correlation NMR spectrum without the need for identification and assignment of individual metabolites. ChemSMP uses a novel indexing and scoring system comprised of a ``uniqueness score'' and a ``coverage score''. Our method is demonstrated on metabolic pathways data from the Small Molecule Pathway Database (SMPDB) and chemical shifts from the Human Metabolome Database (HMDB). Benchmarks show that ChemSMP has a positive prediction rate of >90% in the presence of deduttered data and can sustain the same at 60-70% even in the presence of noise, such as deletions of peaks and chemical shift deviations. The method tested on NMR data acquired for a mixture of 20 amino acids shows a success rate of 93% in correct recovery of pathways. When used on data obtained from the cell lysate of an unexplored oncogenic cell line, it revealed active metabolic pathways responsible for regulating energy homeostasis of cancer cells. Our unique tool is thus expected to significantly enhance analysis of NMIR-based metabolomics data by reducing existing impediments.

Report of the Study Group on “ Fisheries and Ecosystem Response to Recent Regime Shifts”

EXECUTIVE SUMMARY 1. DECADAL-SCALE CLIMATE EVENTS 1.1 Introduction 1.2 Basin-scale Patterns 1.3 Long Time Series in the North Pacific 1.4 Decadal Climate Variability in Ecological Regions of the North Pacific 1.5 Mechanisms 1.6 References 2. COHERENT REGIONAL RESPONSES 2.1 Introduction 2.2 Central North Pacific (CNP) 2.3 California Current System (CCS) 2.4 Gulf of Alaska (GOA) 2.5 Bering Sea and Aleutian Islands 2.6 Western North Pacific (WNP) 2.7 Coherence in Regional Responses to the 1998 Regime Shift 2.8 Climate Indicators for Detecting Regime Shifts 2.9 References 3. IMPLICATIONS FOR THE MANAGEMENT OF MARINE RESOURCES 3.1 Introduction 3.2 Response Time of Biota to Regime Shifts 3.3 Response Time of Management to Regime Shifts 3.4 Provision of Stock Assessment Advice 3.5 Decision Rules 3.6 References 4. SUGGESTED LITERATURE 4.1 Climate Regimes 4.2 Impacts on Lower Trophic Levels 4.3 Impacts on Fish and Higher Trophic Levels 4.4 Impacts on Ecosystems and Possible Mechanisms 4.5 Regimes and Fisheries Management APPENDIX 1: RECENT ECOSYSTEM CHANGES IN THE CENTRAL NORTH PACIFIC A1.1 Introduction A1.2 Physical Oceanography A1.3 Lower Trophic Levels A1.4 Invertebrates A1.5 Fishes A1.6 References APPENDIX 2: RECENT ECOSYSTEM CHANGES IN THE CALIFORNIA CURRENT SYSTEM A2.1 Introduction A2.2 Physical Oceanography A2.3 Lower Trophic Levels A2.4 Invertebrates A2.5 Fishes A2.6 References APPENDIX 3: RECENT ECOSYSTEM CHANGES IN THE GULF OF ALASKA A3.1 Introduction A3.2 Physical Oceanography A3.3 Lower Trophic Levels A3.4 Invertebrates A3.5 Fishes A3.6 Higher Trophic Levels A3.7 Coherence in Gulf of Alaska Fish A3.8 Combined Standardized Indices of Recruitment and Survival Rate A3.9 References APPENDIX 4: RECENT ECOSYSTEM CHANGES IN THE BERING SEA AND ALEUTIAN ISLANDS A4.1 Introduction A4.2 Bering Sea Environmental Variables and Physical Oceanography A4.3 Bering Sea Lower Trophic Levels A4.4 Bering Sea Invertebrates A4.5 Bering Sea Fishes A4.6 Bering Sea Higher Trophic Levels A4.7 Coherence in Bering Sea Fish Responses A4.8 Combined Standardized Indices of Bering Fish Recruitment and Survival Rate A4.9 Aleutian Islands A4.10 References APPENDIX 5: RECENT ECOSYSTEM CHANGES IN THE WESTERN NORTH PACIFIC A5.1 Introduction A5.2 Sea of Okhotsk A5.3 Tsushima Current Region and Kuroshio/Oyashio Current Region A5.4 Bohai Sea, Yellow Sea, and East China Sea A5.5 References (168 page document)

Litter dynamics and phenology of Melaleuca quinquenervia in south Florida

We monitored litterfall biomass at six different sites of melaleuca (Melaleuca quinquenervia (Cav.) S.T. Blake) forested wetlands in South Florida from July 1997 to June 1999. Annual litterfall of melaleuca varied between sites from 6.5 to 9.9 t dry wt ha(-1) yr(1) over the two-year period. Litterfall was significantly higher (p < 0.0001) in scasonally flooded habitats (9.3 t ha(-1) yr(1)) than in non-flooded (7.5 t ha(-1) yr(1)) and permanently flooded habitats (8.0 t ha(-1) yr(1)). Leaf fall was the major component forming 70% of the total litter, woody material 16%, and reproductive material 11%. Phenology of flowering and leaf flush was investigated by examination of the timing and duration of the fall of different plant parts in the litter traps, coupled with monthly field observations during the two-year study. In both years, flowering began in October and November, with peak flowers production around December, and was essentially completed by February and March. New shoot growth began in mid winter after peak flowering, and extended into the spring. Very little new growth was observed in melaleuca forests during the summer months, from May to August, in South Florida. In contrast, the fall of leaves and small wood was recorded in every month of the year, but generally increased during the dry season with higher levels observed from February to April. Also, no seasonality was recorded in the fall of seed capsules, which apparently resulted from the continual self-thinning of small branches and twigs inside the forest stand. In planning management for perennial weeds, it is important to determine the period during its annual growth cycle when the plant is most susceptible to control measures. These phenological data suggest that the appropriate time for melaleuca control in South Florida might be during late winter and early spring, when the plant is most active.

Exchange energy shifts under dense plasma conditions

The variation of the energy interval between the intercombination line ( 1s2p(P-3(1))-> 1s(2)) and the resonance line ( 1s2p(P-1(1))-> 1s(2)) of He-like aluminium with plasma density and temperature is investigated. Since such energy interval is equivalent to the exchange energy of the state 1s2p(P-3(1)), we consider the dependence of this energy shift on the plasma environment. It was found that the shifts of exchange energy increase ( decrease) with the increase of electron density ( electron temperature), and the shifts of exchange energy become more sensitive to the electron density as the electron temperature decreases, i. e. in the strongly coupled plasma regime. An approximately linear relation is found between the shifts of exchange energy and the electron density. The results show that dense plasma effects are very important for the simulation of the spectral fine structure. The relative shifts between the intercombination ( 1s2p(P-3(1))-> 1s(2)) and the resonance line ( 1s2p(P-1(1))-> 1s(2)) are discussed for diagnostic applications.