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.     

Salt Diapirs, Salt Brine Seeps, Pockmarks and Surficial Sediment Creep and Slides in the Canary Channel off NW Africa

Circular to elliptical mounds in the Canary Channel with reliefs of 75 to 375 m and diameters of 4 to 8 km partially surrounded by moats with reliefs of 25 to 75 m, were formed by piercement of the seafloor by Mesozoic evaporites. Several long gullies, < 1km wide, with abrupt terminations and pockmarks associated with these mounds were probably eroded by dense brine and hydrocarbon seeps. The salt brines that eroded the gullies were formed where salt diapirs intersect the seafloor, or in the subsurface by circulating ground water heated by igneous activity along the Canary Ridge. If the brines originated in the subsurface they reached the seafloor along faults. Displacement of the surficial sediments by sliding and creep is probably the result of the expulsion of hydrocarbons and/or vertical motion of the Mesozoic evaporites. Microtopographic features along or near the east flank of the Canary Ridge are the creation of uplift of the ridge, hydrothermal activity, mass wasting processes and turbidity currents.     

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.     

Uncertainty in predictions of oil spill trajectories in open sea

A method is introduced to calculate and to account for the uncertainties in the predictions of oil spill trajectories using a classic oil spill model. The method considers the output of the oil spill model as a function of random variables, which are the input parameters, and calculates the standard deviation of the output results which gives a measure of the uncertainty of the model given the uncertainties of the input parameters.Instead of a single trajectory that is calculated by the oil spill model using the mean values of the parameters, a band of trajectories can be defined when various simulations are done taking into account the uncertainties of the input parameters. This band of trajectories defines envelopes of the trajectories that are likely to be followed by the spill given the uncertainties of the input.The method is applied to an oil spill that occurred in open sea near Madeira Islands, in the Atlantic Ocean, in December 1989. The simulations allow the understanding of how a change in the wind direction drove the spill towards the Islands.The envelope of likely trajectories that is obtained with the uncertainty modelling shows a band of trajectories that is in better agreement with the observations than the single trajectory simulated by the oil spill model, based on mean parameters.     

Reconstruction of sea surface dimethylsulfide in the North Pacific during 1970s to 2000s

We proposed an empirical equation of sea surface dimethylsulfide (DMS, nM) using sea surface temperature (SST, K), sea surface nitrate (SSN, μM) and latitude (L, °N) to reconstruct the sea surface flux of DMS over the North Pacific between 25°N and 55°N: ln DMS = 0.06346 · SST − 0.1210 · SSN − 14.11 · cos(L) − 6.278 (R² = 0.63, p < 0.0001). Applying our algorithm to climatological hydrographic data in the North Pacific, we reconstructed the climatological distributions of DMS and its flux between 25 °N and 55 °N. DMS generally increased eastward and northward, and DMS in the northeastern region became to 2–5 times as large as that in the southwestern region. DMS in the later half of the year was 2–4 times as large as that in the first half of the year. Moreover, applying our algorithm to hydrographic time series datasets in the western North Pacific from 1971 to 2000, we found that DMS in the last three decades has shown linear increasing trends of 0.03 ± 0.01 nM year^− 1 in the subpolar region, and 0.01 ± 0.001 nM year^− 1 in the subtropical region, indicating that the annual flux of DMS from sea to air has increased by 1.9–4.8 μmol m^− 2 year^− 1. The linear increase was consistent with the annual rate of increase of 1% of the climatological averaged flux in the western North Pacific in the last three decades.     

Impact of urban stormwater runoff on estuarine environmental quality

Urban stormwater runoff could contribute to the deterioration of water quality of a receiving water body. In this research, field studies and laboratory experiments were conducted to assess the microbial contamination resulting from urban stormwater runoff into the Lake Pontchartrain estuary. Fecal coliform, Escherichia coli and enterococci were used as indicator organisms. The specific objectives of the research were to examine the distribution of the indicator organisms in different environmental elements (water column, suspended particles and sediment) and to further investigate the mechanisms related to their fate. Results of the research indicated satisfactory water quality at the study sites during dry weather periods. However, a significant increase was observed in the concentrations of the indicator organisms in the water columns and sediment at specific study sites following a given stormwater event. Three to seven days were needed for the elevated indicator organisms to return back to their background levels in the water column and sediment, respectively. The mechanism of sedimentation contributed to a reduction in the microbial concentration in the water column, as the indicator organisms were found to attach to the suspended particles in the stormwater. The percentage of fecal coliform, E. coli and enterococci attached to the suspended particles was found to be within the range of 9.8–27.5%, 21.8–30.4%, and 8.4–11.5% of the total indicator organisms in the stormwater loaded into the estuary, respectively. About 75–80% of the total indicator organisms remained free-floating for some distance in the water column before dying off.     

Composition and distribution of meiobenthos in amursky bay (peter the great bay, the east sea)

Qualitative and quantitative composition of meiobenthos was studied in Amursky Bay (Peter the Great Bay, the East Sea). Ten taxonomic groups were found, where nematodes were dominant. Density of meiobenthos in ground sediments of the Bay were not uniform, and the average density was measured at 126.4±62.3 ind. m^-2. 56 species of nematodes were detected, and dominant species wereSabatieria palmaris, Paracanthonchus macrodon, Sphaerolaimus limosus, S. gracilis andOncholaimium ramosum. Five taxocenes of nematodes were allocated based on the results of cluster analysis and species domination according to density. Low diversity in species composition of nematodes was noted in the northwestern part of the Bay, which is a zone of desalination, and in the eastern part, which is exposed to household drains.     

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.