Importance of the oxidation/maturation pair in the evolution of humic coals

The natural thermal evolution of type III coals (Humic origin) is expressed during diagenesis by a loss of oxygen as CO₂ and H₂O. Other phenomena such as oxidation can cause extensive geochemical modifications and may complicate the effects of simple maturation.Humic coals from the Jurassic in southeastern Utah were studied by elemental analysis, Rock-Eval pyrolysis and infrared spectroscopy. In a van Krevelen diagram (atomic H/C vs atomic O/C), the samples fall within the envelope defined by 860 reference humic coals covering the entire range of diagenesis. Nevertheless, various criteria (geochemical, petrographic, geological and microscopic) cast doubt upon the interpretation that such a distribution of coal composition results from thermal maturation.The same criteria indicate the intervention of redox phenomena. Comparison of our results with those from artificial and natural oxidation shows that these coals were subjected to an oxidation process different from ordinary late alteration. This process was probably due to circulation of highly oxidizing saline water causing oxygen fixation and the transformation of carboxyls into carboxylate anions. The cations that were fixed are oxygenated and certainly contain calcium, but also uranium and perhaps several other cations (V, Mo, Fe...). Emphasis is placed on possible mechanisms that cause such phenomena.     

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6–2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6‰ in¹⁸O during differentiation is explained by crystallization of¹⁸O-depleted mafic phases. Silicic glasses have elevated δ¹⁸O values and relatively low δD values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary δD values of −53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere.     

Comparison between natural and artificial maturation series of humic coals from the Mahakam delta,Indonesia

Type III (humic) organic matter from the Mahakam delta (Indonesia) was chosen to compare artificial and natural coal series. Powdered and concentrated immature organic matter was heated in sealed gold tubes for 24 hr at temperatures ranging from 250 to 550°C and under pressures ranging from 0.5 to 4 kb, with and without water. Both elemental and Rock-Eval analyses were used to characterize the products. A comparison between our results, published data and the natural model shows that, quantitatively, natural maturation is simulated better when pyrolysis is performed under confined conditions (no free volume, no diluting inert gas). Thus, pyrolysis in a medium swept by an inert gas, vacuum pyrolysis and some pyrolysis in sealed glass tubes must be considered to be poor simulation tools. The presence of water does not seem to have an essential effect. Allowing the hydrocarbons formed to reach a certain value of partial pressure seems to be important. Results are unchanged when external pressure varies from 0.5 to 4 kb.     

Geochemistry of silicic magmas in the Macolod Corridor, SW Luzon, Philippines: evidence of distinct, mantle-derived, crustal sources for silicic magmas

Silicic volcanic deposits (>65 wt% SiO₂), which occur as domes, lavas and pyroclastic deposits, are relatively abundant in the Macolod Corridor, SW Luzon, Philippines. At Makiling stratovolcano, silicic domes occur along the margins of the volcano and are chemically similar to the silicic lavas that comprise part of the volcano. Pyroclastic flows are associated with the Laguna de Bay Caldera and these are chemically distinct from the domes and lavas at Makiling stratovolcano. As a whole, samples from the Laguna de Bay Caldera contain lower concentrations of MgO and higher concentrations of Fe₂O_3(t) than the samples from domes and lavas. The Laguna de Bay samples are more enriched in incompatible trace elements. The silicic rocks from the domes, Makiling Volcano and Laguna de Bay Caldera all contain high alkalis and high K₂O/Na₂O ratios. Melting experiments of primitive basalts and andesites demonstrate that it is difficult to produce high K₂O/Na₂O silicic magmas by fractional crystallization or partial melting of a low K₂O/Na₂O source. However, recent melting experiments (Sisson et al., Contrib Mineral Petrol 148:635–661, 2005) demonstrate that extreme fractional crystallization or partial melting of K-rich basalts can produce these silicic magmas. Our model for the generation of the silicic magmas in the Macolod Corridor requires partial melting of mantle-derived, evolved, moderate to K-rich, crystallized calc-alkaline magmas that ponded and crystallized in the mid-crust. Major and trace element variations, along with oxygen isotopes and ages of the deposits, are consistent with this model. Electronic Supplementary Material Supplementary material is available for this article at     

Changes to sediment sources following wildfire in a forested upland catchment,southeastern Australia

Few investigations link post‐fire changes to sediment sources and erosion processes with sediment yield response at the catchment scale. This linkage is essential if downstream impacts on sediment transport after fire are to be understood in the context of fire effects across different forest environments. In this study, we quantify changing source contributions to fine sediment (<63 µm) exported from a eucalypt forest catchment (136 ha) burnt by wildfire. The study catchment is one of a pair of research catchments located in the East Kiewa River valley in southeastern Australia that have been the subject of a research program investigating wildfire effects on runoff, erosion, and catchment sediment/nutrient exports. This previous research provided the opportunity to couple insights gained from a range of measurement techniques with the application of fallout radionuclides ¹³⁷Cs and ²¹⁰Pb_ex to trace sediment sources. It was found that hillslope surface erosion dominated exports throughout the 3·5‐year post‐fire measurement period. During this time there was a pronounced decline in the proportional surface contribution from close to 100% in the first six months to 58% in the fourth year after fire. Over the study period, hillslope surface sources accounted for 93% of the fine sediment yield from the burnt catchment. The largest decline in the hillslope contribution occurred between the first and second years after fire, which corresponded with the previously reported large decline in sediment yield, breakdown of water repellency in burnt soils, substantial reduction in hillslope erodibility, and rapid surface vegetation recovery. Coupling the information on sediment sources with hillslope process measurements indicated that only a small proportion of slopes contributed sediment to the catchment outlet, with material derived from near‐channel areas dominating the post‐fire catchment sediment yield response. Copyright © 2011 John Wiley & Sons, Ltd.     

High-resolution mass spectrometric characterization of dissolved organic matter from warm and cold periods in the NEEM ice core

Dissolved organic matter(DOM) is an important component of ice cores but is currently poorly characterized. DOM from one Holocene sample(HS, aged at 1600–4500 B.P.) and one Last Glacial Maximum sample(LS, aged at 21000–25000 B.P.) from the North Greenland Eemian Ice Drilling(NEEM) ice core were analyzed by ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR-MS). CHO compounds contributed 50% of the compounds identified in negative-ionization mode in these two samples, with significant contributions from organic N, S, and P compounds, likely suggesting that marine DOM was an important source in these samples. Overall, the chemical compositions are similar between these two samples, suggesting their consistent DOM sources. However, subtle differences in the DOM between these two samples are apparent and could indicate differences in source strength or chemistry occurring through both pre-and post-depositional processes. For example, higher relative amounts of condensed carbon compounds in the HS DOM(5%), compared to the LS DOM(2%), suggest potentially important contributions from terrestrial sources. Greater incorporation of P in the observed DOM in the LS DOM(22%), compared to the HS DOM(13%), indicate more active microbiological processes that likely contribute to phosphorus incorporation into the DOM pool. Although these two samples present only a preliminary analysis of DOM in glacial/interglacial periods, the data indicate a need to expand the analysis into a broader range of ice-core samples, geographical locations, and glacial/interglacial periods.