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.     

Phototoxicity of pyrene and benzo[a]pyrene to embryo-larval stages of the Pacific oyster Crassostrea gigas

There is a growing body of evidence to suggest that certain polycyclic aromatic hydrocarbons (PAHs) pose a greater hazard to aquatic organisms than previously demonstrated, due to their potential to cause photo-induced toxicity when exposed to ultraviolet (UV) radiation. The consequences of photo-induced toxicity are reported here for embryo-larval stages of the pacific oyster Crassostrea gigas, following exposure to pyrene and benzo[a]pyrene. During laboratory investigations, significant increases in toxicity were observed in the presence of environmentally attainable levels of UV-radiation, compared with embryos exposed to PAH alone, at levels previously deemed to have little acute biological effect. The phototoxicity of pyrene and benzo[a]pyrene completely inhibited the development to the D-shell larval stage when embryos were simultaneously exposed to 5 microg l(-1) PAH and ultraviolet light (UVB = 6.3 +/- 0.1 microW/cm2 and UVA = 456.2 +/- 55 microW/cm2). A linear relationship was also demonstrated for benzo[a]pyrene phototoxicity with decreasing UV light intensity.     

Temperature fluctuations in the atmospheric surface layer over the thermally inhomogeneous underlying surface

The influence of both spatial and temporal temperature inhomogeneities of the underlying surface on the temperature field in an unstably stratified atmospheric surface layer is considered. The methods of correlation and spectral analyses are proposed to estimate statistical characteristics of surface-air temperature fluctuations caused by both turbulent mixing and inhomogeneities in the temperature of the underlying surface. Analysis of experimental data obtained from measurements in the atmospheric surface layer yields estimates for the contribution made by the time-dependent thermal properties of the underlying surface to the total variance of air-temperature fluctuations. It is shown that the additional air-temperature fluctuations generated by surface-temperature inhomogeneities and unrelated to shear flow may reach 70% and 30% of the total variance of measured fluctuations under variable cloudiness and clear skies, respectively. For the height z = 2 m within the wave-number range 2 × 10^?3 rad m^?1 < k < 0.1 rad m^?1, the contribution made by a spatial surface-temperature inhomogeneity to the variance of air-temperature fluctuations does not exceed 10% of the total variance. Correlation and spectral analyses of experimental data make it possible to isolate the spectra of properly turbulent fluctuations from the measured fluctuations and thus to obtain more accurate values of the universal function of similarity theory for temperature in the range of small wave numbers beyond the inertial range.     

Path following control system for a tanker ship model

A two-dimensional path following control system for autonomous marine surface vessels is presented. The guidance system is obtained through a way-point guidance scheme based on line-of-sight projection algorithm and the speed controller is achieved through state feedback linearization. A new approach concerning the calculation of a dynamic line-of-sight vector norm is presented which main idea is to improve the speed of the convergence of the vehicle to the desired path. The results obtained are compared with the traditional line-of-sight scheme. It is intended that the complete system will be tested and implemented in a model of the “Esso Osaka” tanker. The results of simulations are presented here showing the effectiveness of the system aiming in to be robust enough to perform tests either in tanks or lakes.     

Time domain modelling of the transient asymmetric flooding of Ro-Ro ships

This work aims at contributing to improve knowledge on transient asymmetric flooding through theoretical and experimental research. First, a time domain theoretical model of ship motions and flooding is described. Results from experimental work are presented evidencing that transient asymmetric flooding may cause the capsizing of a Ro-Ro shaped barge. The theoretical model is used to predict the capsize of the Ro-Ro shaped barge. Reasonable agreement between experimental and theoretical results was found. Finally, a review of the European Gateway accident is given and the theoretical model is applied to the study of this type of accident. The conclusion is that this theoretical model, together with an accurate modelling of the flooding of machinery compartments, reproduces successfully the capsizing of the European Gateway due to transient asymmetric flooding. Therefore, the internal arrangement of Ro-Ro ships should be carefully studied at the design stage in order to avoid this phenomenon.     

A simplified model for the transformation of the atmospheric planetary boundary layer overlying a thermal front in the sea

This paper discusses a simplified model for the evolution of the atmospheric planetary boundary layer overlying a thermal front in the sea. The model provides local values of the friction/heat transfer geostrophic coefficients and the direction of surface wind stress, as well as the wind/temperature profiles at any point on the front. With the running over a warm front, the baroclinicity of the internal boundary layer leads to the generation of a near-surface current of air directed down the front. The model can be used to interpret radar imagery of the sea surface with the purpose of determining its mesoscale variability. Translated by Vladimir A. Puchkin.     

Quantitative distribution of meiobenthos in deep-water zones of the World Ocean

An analysis of published and original data on the meiobenthos abundance in the depth interval from 100 to 9807 m (in total, 665 records, 445 of them obtained for depths exceeding 1000 m) revealed general regularities in its distribution. The influence of the sampling and data processing methods on the quantitative estimates of the meiobenthos abundance is considered to demonstrate changes in the proportions of the main meiobenthic taxa at different depths and to characterize latitudinal changes in the meiobenthos abundance. The dependence of the abundance of free-living nematodes, the most abundant group of metazoan meiobenthos, on trophic conditions is analyzed. No significant differences in the meiobenthos abundance in the samples obtained by box-and multicorers are established. It is shown that the share of nematodes in metazoan meiobenthos communities increases with the depth. In temperate latitudes, a distinct maximum in the population density confined to depths exceeding 1 km is observed. The quantitative distribution of the meiobenthos at the depths gradient is controlled by the bottom macrotopography and trophic conditions.     

Summer distribution and geochemical composition of suspended-particulate matter in the east china sea

The distribution and geochemical composition of suspended-particulate matter (SPM) in the East China Sea (ECS) were investigated during the summer period of high continental runoff to elucidate SPM sources, distribution and cross-shelf transport. The spatial variability of SPM distribution (0.3–6.5 mg l⁻¹) and geochemical composition (POC, Al, Si, Fe, Mn, Ca, Mg and K) in the ECS was pronounced during summer when the continental fluxes of freshwater and terrestrial materials were highest during the year. Under the influences of Changjiang runoff, Kuroshio intrusion, surface production and bottom resuspension, the distribution generally showed strong gradients decreasing seaward for both biogenic and lithogenic materials. Particulate organic carbon was enriched in surface water (mean ∼18%) due to the influence of biological productivity, and was diluted by resuspended and/or laterally-transported materials in bottom water (mean 9.4%). The abundance of lithogenic elements (Al, Si, Fe, Mn) increased toward the bottom, and the distribution correlations were highly significant. Particulate CaCO₃ distribution provided evidence that the SPM of the bottom water in the northern part of the study area was likely mixed with sediments originally derived from Huanghe. A distinct benthic nepheloid layer (BNL) was present in all seaward transects of the ECS shelf. Sediment resuspension may be caused by tidal fluctuation and other forcing and be regarded as the principal agent in the formation of BNL. This BNL was likely responsible for the transport of biogenic and lithogenic particles across or along the ECS shelf. Total inventories of SPM, POC and PN are 46, 2.8 and 0.4 Tg, respectively, measured over the total area of 0.45 × 10⁶ km² of the ECS shelf. Their mean residence times are about 27, 13 and 11 days, respectively. The inventory of SPM in the water column was higher in the northernmost and southernmost transects and lower in the middle transects, reflecting the influences of terrestrial inputs from Changjiang and/or resuspended materials from Huanghe deposits in the north and perhaps from Minjiang and/or Taiwan’s rivers in the south. The distribution and transport patterns of SPM and geochemical elements strongly indicate that continental sources and cross-shelf transport modulate ECS particulate matter in summer.