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.     

Imposex still evident in eastern Australia 10 years after tributyltin restrictions

A survey of imposex in Thais orbita (Neogastropoda) along the New South Wales (NSW) coast, Australia, found imposex was still widespread 10 years after a partial ban on tributyltin (TBT) based antifouling paints. Transplant experiments also revealed that imposex was induced in T. orbita over a period of 9 weeks in Sydney Harbour, NSW. A comparison of the imposex data with that collected shortly after the introduction of restrictions on TBT revealed a general decline in imposex frequency occurring at open coast sites, an exception being the site at South West Rocks. Sites located within harbour/bay areas did not display a decline in imposex frequency but a decline in the severity of imposex was apparent. The observed decrease in imposex values in T. orbita may reflect a general decrease of butyltin contamination within the coastal environment. However, the persistence of contamination "hotspots" within harbours and bays remains a concern.     

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.     

Cycling the representer algorithm for variational data assimilation with a nonlinear reduced gravity ocean model

The representer method was used by [Ngodock, H.E., Jacobs, G.A., Chen, M., 2006. The representer method, the ensemble Kalman filter and the ensemble Kalman smoother: a comparison study using a nonlinear reduced gravity ocean model. Ocean Modelling 12, 378–400] in a comparison study with the ensemble Kalman filter and smoother involving a 1.5 nonlinear reduced gravity idealized ocean model simulating the Loop Current (LC) and the Loop Current eddies (LCE) in the Gulf of Mexico. It was reported that the representer method was more accurate than its ensemble counterparts, yet it had difficulties fitting the data in the last month of the 4-month assimilation window when the data density was significantly decreased. The authors attributed this failure to increased advective nonlinearities in the presence of an eddy shedding causing the tangent linear model (TLM) to become inaccurate. In a separate study [Ngodock, H.E., Smith, S.R., Jacobs, G.A., 2007. Cycling the representer algorithm for variational data assimilation with the Lorenz attractor. Monthly Weather Review 135 (2), 373–386] applied the cycling representer algorithm to the Lorenz attractor and demonstrated that the cycling solution was able to accurately fit the data within each cycle and beyond the range of accuracy of the TLM, once adjustments were made in the early cycles, thus overcoming the difficulties of the non-cycling solution. The cycling algorithm is used here in assimilation experiments with the nonlinear reduced gravity model. It is shown that the cycling solution overcomes the difficulties encountered by the non-cycling solution due to a limited time range of accuracy of the TLM. Thus, for variational assimilation applications where the TLM accuracy is limited in time, the cycling representer becomes a very powerful and attractive alternative, given that its computational cost is significantly lower than that of the non-cycling algorithm.     

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.