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 application of GPR to barrier-lagoon sedimentation study in Boao of Hainan Island

Sedimentary successions and internal structure of the coastal barrier-lagoon system of Boao, eastern Hainan Island were studied through utilizing data from test holes and trenches and ground-penetrating-radar (GPR) profiles. During late Pleistocene, fluvial and delta plains developed over an unevenly eroded bedrock during low sea level stand, followed by the formation of littoral and lagoon facies and defined coastal barrier-lagoon-estuary system during the post-glacial uppermost Pleistocene-lower Holocene eustatic rise of the sea level, and the upper Holocene high stand. GPR results show that Yudaitan, a sandy coastal bar backed by a low-laying land (shoal) just east of the active lagoon, is a continuous, parallel and slightly-wavy reflectors indicating homogeneous sandy or sandy gravel sediments, and inclined reflectors partly caused by progradation and accumulation of beach sand and gravel. Quasi-continuous, hummocky and chaotic reflectors from the shoal of Nangang village correspond to mixed accumula     

The application of GPR to barrier-lagoon sedimentation study in Boao of Hainan Island

Sedimentary successions and internal structure of the coastal barrier-lagoon system of Boao, eastern Hainan Island were studied through utilizing data from test holes and trenches and ground-penetrating-radar (GPR) profiles. During late Pleistocene, fluvial and delta plains developed over an unevenly eroded bedrock during low sea level stand, followed by the formation of littoral and lagoon facies and defined coastal barrier-lagoon-estuary system during the post-glacial uppermost Pleistocene-lower Holocene eustatic rise of the sea level, and the upper Holocene high stand. GPR results show that Yudaitan, a sandy coastal bar backed by a low-laying land (shoal) just east of the active lagoon, is a continuous, parallel and slightly-wavy reflectors indicating homogeneous sandy or sandy gravel sediments, and inclined reflectors partly caused by progradation and accumulation of beach sand and gravel. Quasi-continuous, hummocky and chaotic reflectors from the shoal of Nangang village correspond to mixed accumulation of sands and clay. This research indicates the GPR is a non-intrusive, rapid, and economical method for high-resolution profiling of subsurface sediments in sandy gravelly coast.     

海南博螯沿岸地貌与人类活动的潜在影响

The Boao coastal system along the eastern coast of Hainan Island is a dynamic delta-tidal inlet-barrier formed during the late Holocene. The delta developed inside a shallow lagoon barred by a sandy barrier with a narrow, shallow tidal inlet opening. Two major distributary channels separated by small islands characterize the delta. The lagoon is silting up receiving and trapping sediments from both the river and, in minor measure during storms, through the tidal inlet opening and barrier washovers. The barrier at the tidal inlet is highly dynamic and changes its form, accreting (migrating spit) against the inlet during fair-weather conditions and being eroded during storms and river floods.The delta has almost completely filled the lagoon and major concerns exist on the effect that ongoing large development plans may have on the environment. These concerns include the effect on floods and rate of siltation once banks of the islands have been stabilized and floodwater and sediment load are impeded from spreading over the lowlands, and the effect of increasing pollutant loads from the new facilities on the ecosystems of the increasingly restricting lagoon water and on the seashores.     

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.     

Site response using coda-wave techniques: Applications to short period data from central and southern Italy

The method of coda waves was applied to two different sets of data for the evaluation of the relative site response.The first set of data consists of low magnitude earthquakes with closely spaced locations, recorded at a small aperture array of velocimeters located in the Abruzzo region, central Italy. The second set of data is composed of events with epicentral distance ranging from 20 to 300 km, recorded at a seismological network with an aperture of about 100 km located in the Puglia region, southern Italy.Results show that the coda wave method furnishes stable estimates of the site effect. An amplification, relative to an arbitrary site, of a factor of about 2 occurs in the 1.7–6 Hz frequency band for two stations of the Abruzzo network, while an amplification factor of about 0.5 occurs in the whole frequency band (1–24 Hz) for one of the stations of the Puglia network. This station is located in an area which is correlated with a low macroseismic intensity anomaly.     

Error analysis in hypocentral locations at Phlegraean Fields

The location reliability of the earthquakes occurred at Phlegraean Fields has been analyzed, and the theoretical errors, inferred from the diagonal elements of the covariance matrix, have been estimated. Using only first P-phase arrivals to the local network (22 stations) and assuming a reading error of 0.05 sec., the average error on the spatial coordinates is estimated to be of the order of 0.2 km.Shallow events (depth<1 km) are very poorly constrained in depth at the borders of the network. The use of both P and S arrival times, recorded by a smaller three component network (10 stations), improves the depth determination.Further analysis has been performed on a set of about 350 selected earthquakes, using two different velocity models.Differences in depth considerably greater than the theoretical errors, and showing highly different patterns have been found.Tests with artificial events, randomly distributed in space, indicate that the observed depth distribution is essentially due to the used velocity model.     

Considérations sur le volcanisme post-ophiolitique dans les Alpes occidentales

Résumé L'activité magmatique ophiolitique du géosynclinal alpin (diabases, gabbros, serpentines, etc.) a été suivie par une activité à caractère volcanique moins bien connue. En effet, les appareils correspondant à cette activité ont complètement disparu; nous devons nous contenter pour tous renseignements de l'étude des fragments de roches contenus dans des grauwackes tertiaires appartenant au Flysch (grès de Taveyanne, grès d'AItdorf pro parte, grès du Champsaur).La détermination de la nature originelle des laves est, en outre, rendue difficile par le fait, découvert récemment, que ces grauwackes ont subi un métamorphisme régional les plaçant dans le faciès à zéolites; on peut raisonnablement admettre qu'il s'agissait d'andésites basaltiques.L'áge des épanchements est encore indéterminé, il doit être compris entre le Crétacé supérieur et la fin de l'Eocène. L'hypothèse la plus plausible consiste à admettre que les volcans, aujourd'hui complètement érodés se trouvaient dans la partie la plus interne du domaine pennique. Toutefois au moment du dépôt des grès de Taveyanne, les coulées ne se trouvaient plus dans leur position initiale, elles avaient glissé vers l'avant-pays sous forme d'une nappe.Il est très probable que cette activité volcanique post-ophiolitique n'est pas restreinte au segment franco-suisse des Alpes occidentales mais que des formations analogues aux grès de Taveyanne se retrouvent ailleurs, notamment en Sicile et dans les Apennins.

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The magmatic activity which gave birth to the ophiolites (diabases, gabbros, serpentinites) of the alpine geosyncline was followed by subaerial volcanism. This volcanic activity is not well known as the volcanoes were completely destroyed by erosion. Our only source of information is to be found in fragments of volcanic rocks which are part of Tertiary Flysch graywackes (Taveyanne sandstones, part of the Altorf sandstones, Champsaur sandstones).The determination of the initial composition of the lavas is further complicated by metasomatic transformations; it has been recently shown that the Taveyanne graywackes were submitted to a light regional metamorphism corresponding to the zeolitic facies ofCoombs. However, it seems that these lavas were originally basaltic andesites.The age of this volcanism is not precisely known, it cannot be later than Upper Eocene as the time of deposition of the Taveyanne sandstones is Uppermost Eocene-Lower Oligocene; it is probably post-Cenomanian. It is likely that the volcanoes were located in the southern part of the Penninic zone; however at the time of deposition of the graywackes the volcanic flows had already left their initial location, gliding toward the Foreland as part of a Nappe.Very probably, remnants of this post-ophiolitic volcanism are not restricted to the French-Swiss segment of the Western Alps, but will be found elsewhere, particularly in the Apennine Mountains and in Sicily.

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Zusammenfassung Die magmatische Tätigkeit, die Ophiolithe (Diabase, Gabbros, Serpentinite) der alpinen Geosynklinale entstehen ließ, wurde von subärischem Vulkanismus abgelöst. Diese Vulkantätigkeit ist wenig bekannt, da die Vulkane durch Erosion völlig zerstört wurden. Unsere einzige Informationsquelle findet sich in vulkanischen Gesteinsfragmenten, die Bestandteile der Tertiär-Flysch-Grauwacken sind.Die Bestimmung der ursprünglichen Zusammensetzung der Laven wird weiter durch metasomatische Umwandlungen erschwert. Kürzlich wurde gezeigt, daß die Taveyanne-Grauwacken einem regionalen Metamorphismus ausgesetzt waren, welcher der zeolithischen Fazies von Coombs entspricht. Es scheint jedoch, daß diese Laven ursprünglich basaltische Andésite waren.Das Alter dieses Vulkanismus ist nicht genau bekannt; es kann aber nicht später sein als das Obere Eozän, da die Ablagerungszeit der Taveyanne-Sandsteine Oberstes Eozän—Unteres Oligozän ist. Wahrscheinlich lagen die Vulkane im südlichen Teil der penninischen Zone; zur Zeit der Ablagerung der Grauwacken waren die Vulkanite bereits in die Überschiebungsmassen mit einbezogen.Sehr wahrscheinlich sind die Überreste dieses nach-ophiolithischen Vulkanismus nicht auf den französisch-schweizerischen Abschnitt der Westalpen beschränkt, sondern werden sich auch andernorts speziell auf dem Apennin und in Sizilien finden lassen.

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