Can density functional theory (DFT) be used as an aid to a deeper understanding of tandem mass spectrometric fragmentation pathways?

Prediction of tandem mass spectrometric (MS/MS) fragmentation for non-peptidic molecules based on structure is of immense interest to the mass spectrometrist. If a reliable approach to MS/MS prediction could be achieved its impact within the pharmaceutical industry could be immense. Many publications have stressed that the fragmentation of a molecular ion or protonated molecule is a complex process that depends on many parameters, making prediction difficult. Commercial prediction software relies on a collection of general heuristic rules of fragmentation, which involve cleaving every bond in the structure to produce a list of 'expected' masses which can be compared with the experimental data. These approaches do not take into account the thermodynamic or molecular orbital effects that impact on the molecule at the point of protonation which could influence the potential sites of bond cleavage based on the structural motif. A series of compounds have been studied by examining the experimentally derived high-resolution MS/MS data and comparing it with the in silico modelling of the neutral and protonated structures. The effect that protonation at specific sites can have on the bond lengths has also been determined. We have calculated the thermodynamically most stable protonated species and have observed how that information can help predict the cleavage site for that ion. The data have shown that this use of in silico techniques could be a possible way to predict MS/MS spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

Towards Data Management Planning Support for Research Data

Görzig, H., Engel, F., Brocks, H., Vogel, T. & Hemmje, M. (2015, August). Towards Data Management Planning Support for Research Data. Paper presented at the ASE International Conference on Data Science, Stanford, United States of America.

Using continuous plankton recorder data

The continuous plankton recorder (CPR) survey is the largest multi-decadal plankton monitoring programme in the world. It was initiated in 1931 and by the end of 2004 had counted 207,619 samples and identified 437 phyto- and zooplankton taxa throughout the North Atlantic. CPR data are used extensively by the research community and in recent years have been used increasingly to underpin marine management. Here, we take a critical look at how best to use CPR data. We first describe the CPR itself, CPR sampling, and plankton counting procedures. We discuss the spatial and temporal biases in the Survey, summarise environmental data that have not previously been available, and describe the new data access policy. We supply information essential to using CPR data, including descriptions of each CPR taxonomic entity, the idiosyncrasies associated with counting many of the taxa, the logic behind taxonomic changes in the Survey, the semi-quantitative nature of CPR sampling, and recommendations on choosing the spatial and temporal scale of study. This forms the basis for a broader discussion on how to use CPR data for deriving ecologically meaningful indices based on size, functional groups and biomass that can be used to support research and management. This contribution should be useful for plankton ecologists, modellers and policy makers that actively use CPR data.

The importance of high frequency data in ecological modelling.

The purpose of this note is to discuss the role of high frequency data in ecological modelling and to identify some of the data requirements for the further development of ecological models for operational oceanography. There is a pressing requirement for the establishment of data acquisition systems for key ecological variables with a high spatial and temporal coverage. Such a system will facilitate the development of operational models. It is envisaged that both in-situ and remotely sensed measurements will need to combined to achieve this aim.

The global distribution of phytoplankton size spectrum and size classes from their light-absorption spectra derived from satellite data

The absorption spectra of phytoplankton in the visible domain hold implicit information on the phytoplankton community structure. Here we use this information to retrieve quantitative information on phytoplankton size structure by developing a novel method to compute the exponent of an assumed power-law for their particle-size spectrum. This quantity, in combination with total chlorophyll-a concentration, can be used to estimate the fractional concentration of chlorophyll in any arbitrarily-defined size class of phytoplankton. We further define and derive expressions for two distinct measures of cell size of mixed. populations, namely, the average spherical diameter of a bio-optically equivalent homogeneous population of cells of equal size, and the average equivalent spherical diameter of a population of cells that follow a power-law particle-size distribution. The method relies on measurements of two quantities of a phytoplankton sample: the concentration of chlorophyll-a, which is an operational index of phytoplankton biomass, and the total absorption coefficient of phytoplankton in the red peak of visible spectrum at 676 nm. A sensitivity analysis confirms that the relative errors in the estimates of the exponent of particle size spectra are reasonably low. The exponents of phytoplankton size spectra, estimated for a large set of in situ data from a variety of oceanic environments (similar to 2400 samples), are within a reasonable range; and the estimated fractions of chlorophyll in pico-, nano- and micro-phytoplankton are generally consistent with those obtained by an independent, indirect method based on diagnostic pigments determined using high-performance liquid chromatography. The estimates of cell size for in situ samples dominated by different phytoplankton types (diatoms, prymnesiophytes, Prochlorococcus, other cyanobacteria and green algae) yield nominal sizes consistent with the taxonomic classification. To estimate the same quantities from satellite-derived ocean-colour data, we combine our method with algorithms for obtaining inherent optical properties from remote sensing. The spatial distribution of the size-spectrum exponent and the chlorophyll fractions of pico-, nano- and micro-phytoplankton estimated from satellite remote sensing are in agreement with the current understanding of the biogeography of phytoplankton functional types in the global oceans. This study contributes to our understanding of the distribution and time evolution of phytoplankton size structure in the global oceans.

Parameterisation of bivalve functional traits for mechanistic eco-physiological dynamic energy budget (DEB) models

Mechanistic models such as those based on dynamic energy budget (DEB) theory are emergent ecomechanics tools to investigate the extent of fitness in organisms through changes in life history traits as explained by bioenergetic principles. The rapid growth in interest around this approach originates from the mechanistic characteristics of DEB, which are based on a number of rules dictating the use of mass and energy flow through organisms. One apparent bottleneck in DEB applications comes from the estimations of DEB parameters which are based on mathematical and statistical methods (covariation method). The parameterisation process begins with the knowledge of some functional traits of a target organism (e. g. embryo, sexual maturity and ultimate body size, feeding and assimilation rates, maintenance costs), identified from the literature or laboratory experiments. However, considering the prominent role of the mechanistic approach in ecology, the reduction of possible uncertainties is an important objective. We propose a revaluation of the laboratory procedures commonly used in ecological studies to estimate DEB parameters in marine bivalves. Our experimental organism was Brachidontes pharaonis. We supported our proposal with a validation exercise which compared life history traits as obtained by DEBs (implemented with parameters obtained using classical laboratory methods) with the actual set of species traits obtained in the field. Correspondence between the 2 approaches was very high (>95%) with respect to estimating both size and fitness. Our results demonstrate a good agreement between field data and model output for the effect of temperature and food density on age-size curve, maximum body size and total gamete production per life span. The mechanistic approach is a promising method of providing accurate predictions in a world that is under in creasing anthropogenic pressure.

US NOAA Fisheries and UK SAHFOS CPR surveys: comparison of methods and data

The US National Oceanic and Atmospheric Administration (NOAA) Fisheries Continuous Plankton Recorder (CPR) Survey has sampled four routes: Boston–Nova Scotia (1961–present), New York toward Bermuda (1976–present), Narragansett Bay–Mount Hope Bay–Rhode Island Sound (1998–present) and eastward of Chesapeake Bay (1974–1980). NOAA involvement began in 1974 when it assumed responsibility for the existing Boston–Nova Scotia route from what is now the UK's Sir Alister Hardy Foundation for Ocean Science (SAHFOS). Training, equipment and computer software were provided by SAHFOS to ensure continuity for this and standard protocols for any new routes. Data for the first 14 years of this route were provided to NOAA by SAHFOS. Comparison of collection methods; sample processing; and sample identification, staging and counting techniques revealed near-consistency between NOAA and SAHFOS. One departure involved phytoplankton counting standards. This has since been addressed and the data corrected. Within- and between-survey taxonomic and life-stage names and their consistency through time were, and continue to be, an issue. For this, a cross-reference table has been generated that contains the SAHFOS taxonomic code, NOAA taxonomic code, NOAA life-stage code, National Oceanographic Data Center (NODC) taxonomic code, Integrated Taxonomic Information System (ITIS) serial number and authority and consistent use/route. This table is available for review/use by other CPR surveys. Details of the NOAA and SAHFOS comparison and analytical techniques unique to NOAA are presented.

Diversity of functional groups in the vegetation sandy seashore of the Grande, Anclitas and Caguamas Cays (Jardines de la Reina Archipelago, Cuba)

Sandy shores are known to be extreme ecosystems where the vegetation has evolved many morphological and physiological adaptations for its survival. With the aim of identify possible relationships between the vegetation´s functional diversity with abiotic factors and its corresponding quantification, we collected data on the abundance and richness of the sandy coast vegetation complex in Grande, Anclitas and Caguamas keys. Its flora is largely characterized by the dominance of hemicryptophytes and chamaephytes plants with nanophyllous leaves and displaying dispersal syndromes such as zoochory and anemochory. However, the functional groups´ richness, in the present study, varies from one key to another. Functional diversity is similar between the wet and dry seasons, and its spatial variation is influenced by the interplay of the set of abiotic factors herein studied.

Identifying four phytoplankton functional types from space: An ecological approach

Deriving maps of phytoplankton taxa based on remote sensing data using bio-optical properties of phytoplankton alone is challenging. A more holistic approach was developed using artificial neural networks, incorporating ecological and geographical knowledge together with ocean color, bio-optical characteristics, and remotely sensed physical parameters. Results show that the combined remote sensing approach could discriminate four major phytoplankton functional types (diatoms, dinoflagellates, coccolithophores, and silicoflagellates) with an accuracy of more than 70%. Models indicate that the most important information for phytoplankton functional type discrimination is spatio-temporal information and sea surface temperature. This approach can supply data for large-scale maps of predicted phytoplankton functional types, and an example is shown.

Scale-dependent foraging ecology of a marine top predator modelled using passive acoustic data

1.Understanding which environmental factors drive foraging preferences is critical for the development of effective management measures, but resource use patterns may emerge from processes that occur at different spatial and temporal scales. Direct observations of foraging are also especially challenging in marine predators, but passive acoustic techniques provide opportunities to study the behaviour of echolocating species over a range of scales. 2.We used an extensive passive acoustic data set to investigate the distribution and temporal dynamics of foraging in bottlenose dolphins using the Moray Firth (Scotland, UK). Echolocation buzzes were identified with a mixture model of detected echolocation inter-click intervals and used as a proxy of foraging activity. A robust modelling approach accounting for autocorrelation in the data was then used to evaluate which environmental factors were associated with the observed dynamics at two different spatial and temporal scales. 3.At a broad scale, foraging varied seasonally and was also affected by seabed slope and shelf-sea fronts. At a finer scale, we identified variation in seasonal use and local interactions with tidal processes. Foraging was best predicted at a daily scale, accounting for site specificity in the shape of the estimated relationships. 4.This study demonstrates how passive acoustic data can be used to understand foraging ecology in echolocating species and provides a robust analytical procedure for describing spatio-temporal patterns. Associations between foraging and environmental characteristics varied according to spatial and temporal scale, highlighting the need for a multi-scale approach. Our results indicate that dolphins respond to coarser scale temporal dynamics, but have a detailed understanding of finer-scale spatial distribution of resources.

Marine biodiversity and ecosystem function relationships:the potential for practical monitoring applications

There is an increasing demand for environmental assessments of the marine environment to include ecosystem function. However, existing schemes are predominantly based on taxonomic (i.e. structural) measures of biodiversity. Biodiversity and Ecosystem Function (BEF) relationships are suggested to provide a mechanism for converting taxonomic information into surrogates of ecosystem function. This review assesses the evidence for marine BEF relationships and their potential to be used in practical monitoring applications (i.e. operationalized). Five key requirements were identified for the practical application of BEF relationships: (1) a complete understanding of strength, direction and prevalence of marine BEF relationships, (2) an understanding of which biological components are influential within specific BEF relationships, (3) the biodiversity of the selected biological components can be measured easily, (4) the ecological mechanisms that are the most important for generating marine BEF relationships, i.e. identity effects or complementarity, are known and (5) the proportion of the overall functional variance is explained by biodiversity, and hence BEF relationships, has been established. Numerous positive and some negative BEF relationships were found within the literature, although many reproduced poorly the natural species richness, trophic structures or multiple functions of real ecosystems (requirement 1). Null relationships were also reported. The consistency of the positive and negative relationships was often low that compromised the ability to generalize BEF relationships and confident application of BEF within marine monitoring. Equally, some biological components and functions have received little or no investigation. Expert judgement was used to attribute biological components using spatial extent, presence and functional rate criteria (requirement 2). This approach highlighted the main biological components contributing the most to specific ecosystem functions, and that many of the particularly influential components were found to have received the least amount of research attention. The need for biodiversity to be measureable (requirement 3) is possible for most biological components although difficult within the functionally important microbes. Identity effects underpinned most marine BEF relationships (requirement 4). As such, processes that translated structural biodiversity measures into functional diversity were found to generate better BEF relationships. The analysis of the contribution made by biodiversity, over abiotic influences, to the total expression of a particular ecosystem function was rarely measured or considered (requirement 5). Hence it is not possible to determine the overall importance of BEF relationships within the total ecosystem functioning observed. In the few studies where abiotic factors had been considered, it was clear that these modified BEF relationships and have their own direct influence on functional rate. Based on the five requirements, the information required for immediate ‘operationalization’ of BEF relationships within marine functional monitoring is lacking. However, the concept of BEF inclusion within practical monitoring applications, supported by ecological modelling, shows promise for providing surrogate indicators of functioning.

Applications of Satellite Earth Observations section - NEODAAS: Providing satellite data for efficient research

The NERC Earth Observation Data Acquisition and Analysis Service (NEODAAS) provides a central point of Earth Observation (EO) satellite data access and expertise for UK researchers. The service is tailored to individual users’ requirements to ensure that researchers can focus effort on their science, rather than struggling with correct use of unfamiliar satellite data.

NEODAAS: Providing satellite data for efficient research

The NERC Earth Observation Data Acquisition and Analysis Service (NEODAAS) provides a central point of Earth Observation (EO) satellite data access and expertise for UK researchers. The service is tailored to individual users’ requirements to ensure that researchers can focus effort on their science, rather than struggling with correct use of unfamiliar satellite data.

Ecological equivalence of species within phytoplankton functional groups

1.There are tens of thousands of species of phytoplankton found throughout the tree of life. Despite this diversity, phytoplankton are often aggregated into a few functional groups according to metabolic traits or biogeochemical role. We investigate the extent to which phytoplankton species dynamics are neutral within functional groups. 2.Seasonal dynamics in many regions of the ocean are known to affect phytoplankton at the functional group level leading to largely predictable patterns of seasonal succession. It is much more difficult to make general statements about the dynamics of individual species. 3.We use a 7 year time-series at station L4 in the Western English Channel with 57 diatom and 17 dinoflagellate species enumerated weekly to test if the abundance of diatom and dinoflagellate species vary randomly within their functional group envelope or if each species is driven uniquely by external factors. 4.We show that the total biomass of the diatom and dinoflagellate functional groups is well predicted by irradiance and temperature and quantify trait values governing the growth rate of both functional groups. The biomass dynamics of the functional groups are not neutral and each has their own distinct responses to environmental forcing. Compared to dinoflagellates, diatoms have faster growth rates, and grow faster under lower irradiance, cooler temperatures, and higher nutrient conditions. 5.The biomass of most species vary randomly within their functional group biomass envelope, most of the time. As a consequence, modelers will find it difficult to predict the biomass of most individual species. Our analysis supports the approach of using a single set of traits for a functional group and suggests that it should be possible to determine these traits from natural communities.