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.     

Environmental Factors Contributing to the Development and Demise of a Toxic Dinoflagellate (<Emphasis Type="Italic">Karlodinium veneficum</Emphasis>) Bloom in a Shallow,Eutrophic, Lagoonal Estuary

A dense bloom of the ichthyotoxic dinoflagellate Karlodinium veneficum was discovered in the Neuse River Estuary, North Carolina, on 19 October 2006 and was associated with four subsequent fish kills. Microscopic, photopigment, DNA, and toxicological techniques confirmed bloom identity and toxicity. High-resolution spatio-temporal data from ship-board and fixed automated sampling stations provided a unique opportunity to investigate the environmental conditions that initiated, maintained, and terminated the K. veneficum bloom. Bloom initiation and growth were favored by high nutrient availability and reduced dispersal during the period of declining riverine discharge after Tropical Storm Ernesto. K. veneficum out-competed other co-occurring dinoflagellates, perhaps because of the production of karlotoxins that are known to act as grazing deterrents and to facilitate mixotrophic feeding. Once the bloom was established, small-scale hydrodynamic processes, coupled with vertical migration, concentrated cells along a frontal convergence to high densities (>200,000 cells per milliliter). By 26 October 2006, wind mixing and possible nutrient stress disrupted the bloom. Release of cell-bound toxins during the bloom collapse likely accounted for the associated fish kill events where fish were reported as exhibiting typical symptoms of karlotoxin poisoning. The dynamics of this bloom underscore the tight control of harmful algal blooms by meteorological forcing, hydrology, and sediment nutrient input in this shallow lagoonal estuary.     

Solar gravitational redshift

Wavelengths of solar spectrum lines should be shifted toward the red by the Sun's gravitational field as predicted by metric theories of gravity according to the principle of equivalence. Photographic wavelengths of 738 solar Fe i lines and their corresponding laboratory wavelengths have been studied. The measured solar wavelength minus the laboratory wavelength (_observed) averaged for the strong lines agrees well with the theoretically predicted shift (_theoretical). Studies show that the departures depend on line strength. No dependence of the departures on wavelength was found within the existing data.By studying strong lines over a wide spectral range, velocity shifts caused by the complex motions in the solar atmosphere seem to affect the results in a minimal fashion.     

Application of the QUILF thermobarometer to the peralkaline trachytes and pantellerites of the Eburru volcanic complex, East African Rift, Kenya

The Quaternary Eburru volcanic complex in the south-central Kenya Rift consists of pantelleritic trachytes and pantellerites. The phenocryst assemblage in the trachytes is sanidine + fayalite + ferrohedenbergite + aenigmatite ± quartz ± ilmenite ± magnetite ± pyrrhotite ± pyrite. In the pantellerites, the assemblage is sanidine + quartz + ferrohedenbergite + fayalite + aenigmatite + ferrorichterite + pyrrhotite ± apatite, although fayalite, ferrohedenbergite and ilmenite are absent from more evolved rocks (e.g. with SiO₂ > 71%). QUILF temperature calculations for the trachytes range from 709 to 793 °C and for the pantellerites 668–708 °C, the latter temperatures being among the lowest recorded for peralkaline silicic magmas. The QUILF thermobarometer demonstrates that the Eburru magmas crystallized at relatively low oxidation states (ΔFMQ + 0.5 to − 1.6) for both trachytes and pantellerites. The trachytes and pantellerites evolved along separate liquid lines of descent, the trachytes possibly deriving from a more mafic parent by fractional crystallization and the pantellerites from extreme fractionation of comenditic magmas.     

Wind erosion from military training lands in the Mojave Desert, California, U.S.A.

Military training activities reduce vegetation cover, disturb crusts, and degrade soil aggregates, making the land more vulnerable to wind erosion. The objective of this study was to quantify wind erosion rates for typical conditions at the Marine Corps Air Ground Combat Center, Twentynine Palms, CA, U.S.A. Five Big Spring Number Eight (BSNE) sampler stations were installed at each of five sites. Each BSNE station consisted of five BSNE samplers with the lowest sampler at 0·05 m and the highest sampler at 1·0 m above the soil surface. Once a month, sediment was collected from the samplers for analysis. Occurrence of saltating soil aggregates was recorded every hour using Sensits, one at each site. The site with the most erosion had a sediment discharge of 311 kg m⁻¹ over a period of 17 months. Other sites eroded much less because of significant rock cover or the presence of a crust. Hourly sediment discharge was estimated combining hourly Sensit count and monthly sediment discharge measured using BSNE samplers. More simultaneously measured data are needed to better characterize the relationship between these two and reconstruct a detailed time-series of wind erosion. This measured time-series can then be used for comparison with simulation results from process-based wind erosion models such as the Wind Erosion Prediction System (WEPS), once it has been adapted to the unique aspects of military lands.     

Southeastern U.S. Vegetation Response to ENSO Events (1989–1999)

El Niño/Southern Oscillation (ENSO) is considered one of the most powerful forces driving anomalous global weather patterns. Large-scale seasonal precipitation and temperature changes influenced by ENSO have been examined in many areas of the world. The southeastern United States is one of the regions affected by ENSO events. In this study, remote sensing detection of vegetation response to ENSO phases is demonstrated with one-kilometer biweekly Normalized Difference Vegetation Index (NDVI) data (1989–1999) derived from the Advanced Very High Resolution Radiometer(AVHRR). The impacts of three ENSO phases, cold, warm and neutral, on vegetation were analyzed with a focus on two vegetation cover types, two seasons and two geographic regions within the southeastern U.S. Significant ENSO effects on vegetation were found in cropland and forest vegetation cover types based on image and statistical analysis of the NDVI data. The results indicate that vegetation condition was optimal during the ENSO neutral phase for both agricultural and natural vegetation.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution²³⁰Th_excess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (²³⁰Th), 0.43–1.40 ppm (²³²Th), 0.09–0.49 ppb (²³⁴U) and 1.66–8.24 ppm (²³⁸U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the²³⁰Th_excess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant²³⁰Th_excess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.     

Greenhouse Gas Emissions from Hydroelectric Reservoirs in Tropical Regions

This paper discusses emissions by power-dams in the tropics. Greenhouse gas emissions from tropical power-dams are produced underwater through biomass decomposition by bacteria. The gases produced in these dams are mainly nitrogen, carbon dioxide and methane. A methodology was established for measuring greenhouse gases emitted by various power-dams in Brazil. Experimental measurements of gas emissions by dams were made to determine accurately their emissions of methane (CH₄) and carbon dioxide (CO₂) gases through bubbles formed on the lake bottom by decomposing organic matter, as well as rising up the lake gradient by molecular diffusion.The main source of gas in power-dams reservoirs is the bacterial decomposition (aerobic and anaerobic) of autochthonous and allochthonous organic matter that basically produces CO₂ and CH₄. The types and modes of gas production and release in the tropics are reviewed.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.