Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

The European coastal zone: characterization and first assessment of ecosystem metabolism

The geomorphic, oceanographic, terrestrial and anthropogenic attributes of the European coastal zone are described and published data on ecosystem function (primary production and respiration) are reviewed. Four regions are considered: the Baltic Sea, Mediterranean Sea, Black Sea and the European Atlantic coast including the North Sea. The metabolic database (194 papers) suffers from a non-homogeneous geographical coverage with no usable data for the Black Sea which was therefore excluded from this part of our study. Pelagic gross primary production in European open shelves is, by far, the most documented parameter with an estimated mean of 41 mmol C m⁻² d⁻¹, the lowest value is reported in the Mediterranean Sea (21 mmol C m⁻² d⁻¹) and the highest one in the Atlantic/North Sea area (51 mmol C m⁻² d⁻¹). Microphytobenthic primary production, mostly measured in shallow areas, is extrapolated to the entire 0–200 m depth range. Its contribution to total primary production is low in all regions (mean: 1.5 mmol C m⁻² d⁻¹). Although macrophyte beds are very productive, a regional production estimate is not provided in this study because their geographical distribution along the European coastline remains unknown. Measurements of pelagic community respiration are clearly too sparse, especially below the euphotic zone, to yield an accurate picture of the fate of organic matter produced in the water column. With a mean value of 17 mmol C m⁻² d⁻¹, benthic community respiration consumes approximately 40% of the pelagic organic matter production. Estuaries generally exhibit high metabolic rates and a large range of variation in all parameters, except microphytobenthic primary production. Finally, the problem of eutrophication in Europe is discussed and the metabolic data obtained in the framework of the Land–Ocean Interactions in the Coastal Zone (LOICZ) project are compared with available direct measurements of net ecosystem production.     

Simulation of Hydrophysical Processes in Coastal Regions of the Sea

In the present work, we generalize the results of our investigations in the field of simulation of hydrophysical and ecological processes in coastal regions of various seas and some closed basins. The developed and applied mathematical models and the results of numerical experiments are briefly analyzed.     

Forced Waves in a Bounded Basin with One Thermocline

Within the framework of the linear theory taking into account the action of the Coriolis force, we study waves induced in a continuously stratified fluid with one thermocline by periodic variations of pressure on the free surface. The fluid fills a bounded basin of constant depth. We establish the dependences of the wave amplitudes and wave velocities on the period of disturbing pressure. The sequence of transformations of generated waves from the barotropic character of motion to baroclinic depending on changes in the period of disturbing pressure is studied in detail.     

Application of the Genetic Algorithm to the Problem of Reconstruction of Missing Data

We study the problem of reconstruction (interpolation and extrapolation) of the vertical profiles of hydrochemical and hydrobiological elements according to incomplete sets of data with simultaneous filtration of short-period components based on expansions in empirical orthogonal functions. The genetic algorithm is used to compute the coefficients of expansion of profiles with missing data. We present the results of processing the data arrays on oxygen, chlorophyll A, and biogenic elements collected in the Black Sea in 1982–1993. The mean error of reconstruction of the profiles enables us to conclude that the proposed method has considerable advantages over the conventional approaches.     

Statistical Modeling of Monthly Anomalies of Atmospheric Precipitations for the Region of the Ukraine and Black Sea

The data array accumulated for the period 1946–1995 is used to select the most significant predictor of monthly anomalies of precipitation in the region of the Ukraine and Black Sea, namely, a large-scale circulation in a sector covering the North Atlantic and Europe. Three large-scale predictors (geopotential at a level of 500GPa, sea-level pressure, and the difference between the geopotentials at levels of 500 and 1000GPa) give almost identical results: their correlation with anomalies of precipitation is equal to 0.7–0.8 in winter and 0.4–0.5 in summer. The predominant mechanism of the influence of circulation on precipitations at low frequencies is the response of the trajectories of European cyclones to changes in the upper-tropospheric jet currents in the Atlantic-European sector described as the superposition of the North-Atlantic oscillation and the Eurasian mode. The decomposition of the fields of precipitations and circulation in the eigenmodes of the canonical correlation analysis opens a possibility of direct computation of the monthly average fields of precipitations for the entire territory of the Ukraine and Black Sea region according to the large-scale geopotential fields.     

Validation of a finite difference method for the simulation of vortex-induced vibrations on a circular cylinder

The Karman Vortex Street generated by a circular cylinder is investigated by the numerical solution of the compressible Navier–Stokes equations in the incompressible Mach number range (Mach<0.3) using the Beam and Warming implicit scheme. The agreement with the fully incompressible projection method (Chorin, 1968) is fairly good while convergence time is very much better. The investigation suggests that the compressible Navier–Stokes equations may be used as an efficient alternative to study incompressible flows as well. Mach numbers just below 0.3 are enough to simulate incompressible flow behavior and at the same time do not cause numerical ill-conditioning in the solution. In addition, some relevant features of the vortices generated and carried by the wake of the cylinder could be fairly well captured.     

Structural monitoring of offshore platforms using impulse and relaxation response

Monitoring offshore platforms, long span bridges, high rise buildings, TV towers and other similar structures is essential for ensuring their safety in service. Continuous monitoring assumes even greater significance in the case of offshore platforms, which are highly susceptible to damage due to the corrosive environment and the continuous action of waves. Also, since a major part of the structure is under water and covered by marine growth, even a trained diver cannot easily detect damage in the structure. In the present work, vibration criterion is adopted for structural monitoring of jacket platforms. Artificial excitation of these structures is not always practicable and ambient excitation due to wind and waves may not be sufficient for collecting the required vibration data. Alternate methods can be adopted for the same purpose, for example, the application of an impact or a sudden relaxation of an applied force for exciting the structure. For jacket platforms, impact can be applied by gently pushing the structure at the fender while relaxation can be accomplished by pulling the structure and then suddenly releasing it using a tug or a supply vessel in both cases. The present study is an experimental investigation on a laboratory model of a jacket platform, for exploring the feasibility of adapting vibration responses due to impulse and relaxation, for structural monitoring. Effects of damage in six members of the platform as well as changes in deck masses were studied. A finite element model of the structure was used to analyze all the cases for comparison of the results as well as system identification. A data acquisition and analysis procedure for obtaining the response signatures of the platform due to the impulse and relaxation procedure was also developed for possible adoption in on-line monitoring of offshore platforms. From the study, it has been concluded that both impulse and relaxation responses are useful tools for monitoring offshore jacket platforms. The present work forms the basis for the development of an automated, on-line monitoring system for offshore platforms, using neural networks.     

A singular evolutive extended Kalman filter to assimilate ocean color data in a coupled physical–biochemical model of the North Atlantic ocean

Within the European DIADEM project, a data assimilation system for coupled ocean circulation and marine ecosystem models has been implemented for the North Atlantic and the Nordic Seas. One objective of this project is to demonstrate the relevance of sophisticated methods to assimilate satellite data such as altimetry, surface temperature and ocean color, into realistic ocean models. In this paper, the singular evolutive extended Kalman (SEEK) filter, which is an advanced assimilation scheme where three-dimensional, multivariate error statistics are taken into account, is used to assimilate ocean color data into the biological component of the coupled system. The marine ecosystem model, derived from the FDM model [J. Mar. Res. 48 (1990) 591], includes 11 nitrogen and carbon compartments and describes the synthesis of organic matter in the euphotic zone, its consumption by animals of upper trophic levels, and the recycling of detritic material in the deep ocean. The circulation model coupled to the ecosystem is the Miami isopycnic coordinate ocean model (MICOM), which covers the Atlantic and the Arctic Oceans with an enhanced resolution in the North Atlantic basin. The model is forced with realistic ECMWF ocean/atmosphere fluxes, which permits to resolve the seasonal variability of the circulation and mixed layer properties. In the twin assimimation experiments reported here, the predictions of the coupled model are corrected every 10 days using pseudo-measurements of surface phytoplankton as a substitute to chlorophyll concentrations measured from space. The diagnostics of these experiments indicate that the assimilation is feasible with a reduced-order Kalman filter of small rank (of order 10) as long as a sufficiently good identification of the error structure is available. In addition, the control of non-observed quantities such as zooplankton and nitrate concentrations is made possible, owing to the multivariate nature of the analysis scheme. However, a too severe truncation of the error sub-space downgrades the propagation of surface information below the mixed layer. The reduction of the actual state vector to the surface layers is therefore investigated to improve the estimation process in the perspective of sea-viewing wide field-of-view sensor (SeaWiFS) data assimilation experiments.