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.     

Photobleaching of chromophoric dissolved organic matter in natural waters: kinetics and modeling

The effects of monochromatic and polychromatic UV and visible (VIS) radiation on the optical properties (absorption and fluorescence) of chromophoric dissolved organic matter (CDOM) were examined for a Suwannee River fulvic acid (SRFA) standard and for water from the Delaware and Chesapeake Bays. The primary (direct) loss of absorption and fluorescence occurred at the irradiation wavelength(s), with smaller secondary (indirect) losses occurring outside the irradiation wavelength(s). The efficiency of both direct and indirect photobleaching decreased monotonically with increasing wavelength. Exposure to polychromatic light increased the CDOM absorption spectral slope (S), consistent with previous field measurements. An analysis of the monochromatic photobleaching kinetics argues that a model based on a simple superposition of multiple chromophores undergoing independent photobleaching cannot apply; this conclusion further implies that the absorption spectrum of CDOM cannot arise solely from a simple superposition of the spectra of numerous independent chromophores. The kinetics of CDOM absorption loss with the monochromatic irradiation were employed to create a simple, heuristic model of photobleaching. This model allowed us to examine the importance of the indirect photobleaching losses in determining the overall photobleaching rates as well as to model the photobleaching of natural waters under polychromatic light fields. Application of this model to natural waters closely predicted the change in the CDOM spectral shape caused by photodegradation. The time scale of this process was consistent with field observations acquired during the summertime for coastal waters in the Middle Atlantic Bight (MAB). The results indicate that the ratio of the photodegradation depth to the mixed layer depth is a key parameter controlling the rate of the photobleaching in surface waters.     

Long-Term RST Analysis of Anomalous TIR Sequences in Relation with Earthquakes Occurred in Greece in the Period 2004–2013

Real-time integration of multi-parametric observations is expected to accelerate the process toward improved, and operationally more effective, systems for time-Dependent Assessment of Seismic Hazard (t-DASH) and earthquake short-term (from days to weeks) forecast. However, a very preliminary step in this direction is the identification of those parameters (chemical, physical, biological, etc.) whose anomalous variations can be, to some extent, associated with the complex process of preparation for major earthquakes. In this paper one of these parameters (the Earth’s emitted radiation in the Thermal InfraRed spectral region) is considered for its possible correlation with M ≥ 4 earthquakes occurred in Greece in between 2004 and 2013. The Robust Satellite Technique (RST) data analysis approach and Robust Estimator of TIR Anomalies (RETIRA) index were used to preliminarily define, and then to identify, significant sequences of TIR anomalies (SSTAs) in 10 years (2004–2013) of daily TIR images acquired by the Spinning Enhanced Visible and Infrared Imager on board the Meteosat Second Generation satellite. Taking into account the physical models proposed for justifying the existence of a correlation among TIR anomalies and earthquake occurrences, specific validation rules (in line with the ones used by the Collaboratory for the Study of Earthquake Predictability—CSEP—Project) have been defined to drive a retrospective correlation analysis process. The analysis shows that more than 93 % of all identified SSTAs occur in the prefixed space–time window around (M ≥ 4) earthquake's time and location of occurrence with a false positive rate smaller than 7 %. Molchan error diagram analysis shows that such a correlation is far to be achievable by chance notwithstanding the huge amount of missed events due to frequent space/time data gaps produced by the presence of clouds over the scene. Achieved results, and particularly the very low rate of false positives registered on a so long testing period, seems already sufficient (at least) to qualify TIR anomalies (identified by RST approach and RETIRA index) among the parameters to be considered in the framework of a multi-parametric approach to t-DASH.     

New insights on the origin of troctolites from the breakaway area of the Godzilla Megamullion (Parece Vela back‐arc basin): The role of melt‐mantle interaction on the composition of the lower crust

The troctolites and olivine‐gabbros from the Dive 6 K‐1147 represent the most primitive gabbroic rocks collected at the Godzilla Megamullion, a giant oceanic core complex formed at an extinct spreading segment of the Parece Vela back‐arc basin (Philippine Sea). Previous investigations have shown that these rocks have textural and major elements mineral compositions consistent with a formation through multistage interaction between mantle‐derived melts and a pre‐existing ultramafic matrix. New investigations on trace element mineral compositions basically agree with this hypothesis. Clinopyroxenes and plagioclase have incompatible element signatures similar to that of typical‐MORB. However, the clinopyroxenes show very high Cr contents (similar to those of mantle clinopyroxene) and rim having sharply higher Zr/REE ratios with respect to the core. These features are in contrast with an evolution constrained by fractional crystallization processes, and suggest that the clinopyroxene compositions are controlled by melt‐rock interaction processes. The plagioclase anorthite versus clinopyroxene Mg#[Mg/(Mg + Fe^Tot)] correlation of the Dive 6 K‐1147 rocks shows a trend much steeper than those depicted by other oceanic gabbroic sections. Using a thermodynamic model, we show that this trend is reproducible by fractionation of melts assimilating 1 g of mantle peridotite per 1 °C of cooling. This model predicts the early crystallization of high Mg# clinopyroxene, consistent with our petrological observation. The melt‐peridotite interaction process produces Na‐rich melts causing the crystallization of plagioclase with low anorthite component, typically characterizing the evolved gabbros from Godzilla Megamullion.     

Peculiarities of the Tectonomagmatic Processes in the Interaction Area between the Icelandic Plume and the Bight Transform Fault (North Atlantic)

Doklady Earth Sciences - Geological and geophysical data collected during the 53rd cruise of the R/V Akademik Sergey Vavilov are presented. It is shown that the lateral distribution of the...     

Elastic wave propagation in an irregularly layered medium

The indirect boundary element method (IBEM) is used to simulate wave propagation in two-dimensional irregularly layered elastic media for internal line sources. The method is based on the integral representation for scattered elastic waves using single layer boundary sources. Fulfillment of the boundary conditions leads to a system of integral equations. Results are obtained in the frequency domain and seismograins are computed through Fourier synthesis. In order to test and validate the method we present various comparisons between our results and the time series obtained analytically for a buried line source in a half-space and by using the recently developed spectral element method (SEM).     

New Data on the Structure of the Megatransform System of the Doldrums (Central Atlantic)

Doklady Earth Sciences - The geological and geophysical data acquired during cruise 45 of R/V Akademik Nikolaj Strakhov regarding the structure of the Doldrums megatransform system in the Central...     

Temporal and life history related trends of perfluorochemicals in harbor porpoises from the Danish North Sea

Eighty-five stranded or bycaught harbor porpoises collected from the Danish North Sea between 1980 and 2005 were analyzed for perfluorochemicals in the liver. PFOS was the predominant compound, making up on average 88.9% of the ∑PFC, followed by PFOSA (7.8%). PFUnA (1.9%) and PFDA (1.2%) were detected in most samples. PFHxS, PFNA and PFOA were only found in a minority of the samples. We found substantial differences in PFC concentrations among life history stages, the highest concentrations were found in neonates, suckling juveniles and lactating females. Such differences should be considered when PFC levels in wildlife are evaluated. The high concentrations found in young porpoises are of concern as PFCs have known toxic effects on the development of the central nervous system and reproductive organs. Despite efforts to reduce PFC emissions, a decreasing temporal trend of concentrations was not detected for any compound. PFCA concentrations were found to be increasing.