Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

Low‐temperature concentration of tellurium and gold in continental red bed successions

There is very little understanding of tellurium (Te) distribution and behaviour in sedimentary rocks. A suite of 15 samples of reduction spheroids (centimetre‐scale pale spheroids in otherwise red rock), including samples from eight localities in Triassic red beds across the British Isles, were mapped for Te using Laser Ablation–Inductively Coupled Plasma–Mass Spectrometry. Almost all showed enrichment in Te in the cores of the spheroids relative to background red bed concentrations, by up to four orders of magnitude. Some were also enriched over background in gold and/or mercury. In one case, discrete telluride minerals were recorded. The data show that Te is mobile and can be concentrated in low‐temperature sedimentary environments, controlled by redox variations. The consistency in enrichment across widely separate localities implies that the enrichment is a normal aspect of red bed diagenesis and so likely to be controlled by a ubiquitous process, such as microbial activity.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Using unmanned underwater vehicles as research platforms in coastal ocean studies

The advantages of using unmanned underwater vehicles in coastal ocean studies are emphasized. Two types of representative vehicles, remotely operated vehicle (ROV) and autonomous underwater vehicle (AUV) from University of South Florida, are discussed. Two individual modular sensor packages designed and tested for these platforms and field measurement results are also presented. The bottom classification and albedo package, BCAP, provides fast and accurate estimates of bottom albedos, along with other parameters such as in-water remote sensing reflectance. The real-time ocean bottom optical topographer, ROBOT, reveals high-resolution 3-dimentional bottom topography for target identification. Field data and results from recent Coastal Benthic Optical Properties field campaign, 1999 and 2000, are presented. Advantages and limitations of these vehicles and applications of modular sensor packages are compared and discussed.     

The chemistry of interstellar CH: The contribution of Bates and Spitzer (1951)

We review the present understanding of interstellar CH⁺. We show that the essential chemistry was correctly identified by Bates and Spitzer in 1951. More recent work has been concerned with defining appropriate venues within which this chemistry can function efficiently. This process had led to a much fuller understanding of the nature of the interstellar medium.     

Macroseepage of methane and light alkanes at the La Brea tar pits in Los Angeles

Geologic seepage of methane and light (C₂-C₅) alkanes was measured at the La Brea Tar Pits in Los Angeles. Samples were collected using flux chambers with stainless steel canisters and analyzed using gas chromatography. Average seepage rates from individual seepage sites were 970 ± 330 mg/h of methane, 14.0 ± 5.5 mg/h of ethane, 9.1 ± 3.7 mg/h of propane, 3.7 ± 1.6 mg/h of i-butane, 0.33 ± 0.16 mg/h of n-butane, 260 ± 120 μg/h of i-pentane, and 5.3 ± 1.9 μg/h of n-pentane, while maximum seepage rates exceeded 17 g/h of methane, 270 mg/h of ethane, 190 mg/h of propane, 95 mg/h of i-butane, 10 mg/h of n-butane, 7 mg/h of i-pentane, and 0.1 mg/h of n-pentane. These absolute fluxes have an additional unknown amount of error associated with them due to sampling methodology, and should be taken as the lower limit of emissions. Samples collected revealed generally dry gas, with high methane emissions relative to the light alkanes. Overall emissions from the tar pits were found to come not only from the active geologic seepage, but also from the outgassing of the standing asphalt at the site. Using the gas ratios, which are negligibly affected by errors introduced by sampling methodology, observed in this study, daily emissions of C₂ – C₅ alkanes from the La Brea area were estimated to be 4.7 ± 1.6 Mg, which represents 2–3 % of total emissions in the entire Los Angeles region.     

Sedimentary and faunal events revealed by a revised correlation of post‐glacial Hirnantian (Late Ordovician) strata in the Welsh Basin,UK

The discovery of a previously unrecognized unconformity and of new faunas in the type Llandovery area underpins a revised correlation of Hirnantian strata in mid Wales. This has revealed the sedimentary and faunal events which affected the Lower Palaeozoic Welsh Basin during the global rise in sea level that followed the end‐Ordovician glacial maximum and has allowed their interpretation in the context of local and global influences. In peri‐basinal shelfal settings the onset of post‐glacial deepening is recorded by an unfossiliferous, transgressive shoreface sequence (Cwm Clyd Sandstone and Garth House formations) which rests unconformably on Rawtheyan rocks, deformed during an episode of pre‐Hirnantian tectonism. In the deep water facies of the basin centre, this same sequence boundary is now recognized as the contact between fine‐grained, re‐sedimented mudstones and an underlying regressive sequence of turbidite sandstones and conglomerates; it is at a level lower than previously cited and calls into question the established lithostratigraphy. In younger Hirnantian strata, graptolites associated with the newly recognized Ystradwalter Member (Chwefri Formation) demonstrate that this distal shelf unit correlates with the persculptus graptolite‐bearing Mottled Mudstone Member of the basinal succession. Together these members record an important macrofaunal recolonization of the Welsh Basin and mark a key event in the post‐glacial transgression. Further deepening saw the establishment of a stratified water column and the imposition of anoxic bottom water conditions across the basin floor. These post‐glacial Hirnantian events are consistent with the re‐establishment of connections between a silled Welsh Basin and the open Iapetus Ocean. However, a comparison with other areas suggests that each event records a separate deepening episode within a pulsed glacio‐eustatic transgression, while also reflecting changes in post‐glacial climate and patterns of oceanic circulation and associated biotic flux. British Geological Survey © NERC 2009. All rights reserved.     

Micrometeorological Observations of a Microburst in Southern Finland

On the afternoon of 3 July 2004 in Hyytiälä (Juupajoki, Finland), convective cells produced a strong downburst causing forest damage. The SMEAR II field station, situated near the damage site, enabled a unique micrometeorological analysis of a microburst with differences above and inside the canopy. At the time of the event, a squall line associated with a cold front was crossing Hyytiälä with a reflectivity maximum in the middle of the squall line. A bow echo, rear-inflow notch, and probable mesovortex were observed in radar data. The bow echo moved west-north-west, and its apex travelled just north of Hyytiälä. The turbulence data were analysed at two locations above the forest canopy and at one location at sub-canopy. At 1412 EET (Eastern European Time, UTC+2), the horizontal and vertical wind speed increased and the wind veered, reflecting the arrival of a gust front. At the same time, the carbon dioxide concentration increased due to turbulent mixing, the temperature decreased due to cold air flow from aloft and aerosol particle concentration decreased due to rain scavenging. An increase in the number concentration of ultra-fine particles (< 10 nm) was detected, supporting the new particle formation either from cloud outflow or due to rain. Five minutes after the gust front (1417 EET), strong horizontal and downward vertical wind speed gusts occurred with maxima of 22 and 15 m s^?1, respectively, reflecting the microburst. The turbulence spectra before, during and after the event were consistent with traditional turbulence spectral theory.