The behavior of molybdenum and its isotopes across the chemocline and in the sediments of sulfidic Lake Cadagno, Switzerland

Molybdenum (Mo) isotope studies in black shales can provide information about the redox evolution of the Earth’s oceans, provided the isotopic consequences of Mo burial into its major sinks are well understood. Previous applications of the Mo isotope paleo-ocean redox proxy assumed quantitative scavenging of Mo when buried into sulfidic sediments. This paper contains the first complete suite of Mo isotope fractionation observations in a sulfidic water column and sediment system, the meromictic Lake Cadagno, Switzerland, a small alpine lake with a pronounced oxygen-sulfide transition reaching up to H₂S ∼ 200 μM in the bottom waters (or about 300 μM total sulfide: ΣS²⁻ = H₂S + HS⁻ + S²⁻). We find that Mo behaves conservatively in the oxic zone and non-conservatively in the sulfidic zone, where dissolved Mo concentrations decrease from 14 nM to 2-8 nM across this transition. Dissolved Mo in the upper oxic waters has a δ⁹⁸Mo_oxic = 0.9 ± 0.1‰, which matches that of the riverine input, δ⁹⁸Mo_river = 0.9 ± 0.1‰. In the deeper sulfidic waters, a subaquatic source delivers Mo at 1.55 ± 0.1‰, but the dissolved Mo is even heavier at δ⁹⁸Mo_sulfidic = 1.8‰. Sediment traps in the sulfidic zone of the lake collect particles increasingly enriched in Mo with depth, with δ⁹⁸Mo values significantly fractionated at −0.8‰ to −1.2‰ both near the chemocline and in the deepest trap. Suspended particulates in the sulfidic waters carry lighter Mo than the ambient dissolved Mo pool by ∼0.3-1.5‰. Sedimentary Mo concentrations correlate with total organic carbon and yield Mo levels which are two orders of magnitude higher than typical crustal values found in rocks from the catchment area. Solid-phase Mo in the sediment shows a slightly positive δ⁹⁸Mo trend with depth, from δ⁹⁸Mo = 1.2‰ to 1.4‰ while the pore waters show dramatic enrichments of Mo (>2000 nM) with a relatively light isotope signature of δ⁹⁸Mo = 0.9-1.0‰.These data are explained if Mo is converted to particle-reactive oxythiomolybdates in the sulfidic waters and is fractionated during removal from solution onto particles. Isotope fractionation is expressed in the water column, despite the high sulfide concentrations, because the rate of Mo removal is fast compared to the slow reaction kinetics of thiomolybdate formation. However, elemental and isotopic mass balances show that Mo is indeed quantitatively removed to the lake sediments and thus the isotopic composition of the sediments reflects sources to the sulfidic water. This efficient Mo drawdown is expected to occur in settings where H₂S is very much in excess over Mo or in a restricted setting where the water renewal rate is slow compared to the Mo burial rate. We present a model for the Mo isotope fractionation in sulfidic systems associated with the slow reaction kinetics and conclude that quantitative removal will occur in highly sulfidic and restricted marine systems.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

Geological and geotechnical aspects of underground coal mining methods within Australia

About one quarter of the coal produced in Australia is by underground mining methods. The most commonly used underground coal mining methods in Australia are longwall, and room and pillar. This paper provides a detailed review of the two methods, including their advantages and disadvantages, the major geotechnical and operational issues, and the factors that need to be considered regarding their choice, including the varying geological and geotechnical conditions suited to a particular method. Factors and issues such as capital cost, productivity, recovery, versatility and mine safety associated with the two methods are discussed and compared. The major advantages of the longwall mining method include its suitability for mining at greater depth, higher recovery, and higher production rate compared to room and pillar. The main disadvantages of the room and pillar method are the higher risks of roof and pillar collapse, higher capital costs incurred as well as lower recovery rate.     

Management and stability analysis of a seashore waste landfill site in Korea

Annual variation in the amount and composition of waste deposited in the Gimpo #2 landfill, the largest landfill around Seoul, Korea, is reviewed, and the stability of the same landfill is analyzed during waste disposal. For the stability analysis, three empirical stability prediction methods, i.e., linear stability, displacement velocity, and curve stability methods, are used to analyze field-measured settlement and horizontal displacement data. The analysis indicated that national waste management policy has greatly influenced the annual variation in the amount and composition of waste deposited in the landfill. Continuous measurement of geotechnical data and the use of stability analysis based on these data are necessary for landfills on seashore clay foundation. Stability of the landfill must be examined with various methods to ensure accurate determination of its stability.     

Pre-Breakdown Processes in the Hollow Cathode Region of a Transient Hollow Cathode Discharge

Discharge formation in the A–K space of transient hollow cathode discharge (THCD) is causally linked with the emission of high energy electron beams originating in the hollow cathode region (HCR). Ionization in the A–K gap proceeds through the formation of a moving virtual anode, whose time evolution is strongly correlated with different periods in the electron beam activity. Here, we report on time and space resolved observations of different ionization events inside the HCR, which are time correlated with ionization processes inside the A–K gap. The experiments have been performed in Hydrogen, at pressures between 50 and 400 mTorr. A statistical study of the characteristic times associated with the different ionization events, based on von Laue plots, shows that the time distribution of events is well described by a single Gaussian distribution.     

Holocene relative sea level changes in the Västervik-Gamlebyviken region on the southeast coast of Sweden,southern Baltic Sea

We reconstruct the Holocene shore displacement of the Västervik-Gamlebyviken area on the southeast coast of Sweden, characterised by a maritime cultural landscape and archaeological significance since the Mesolithic. Sediment cores were retrieved from four lake basins that have been raised above sea level due to the postglacial land uplift and eustatic sea level changes after the melting of the Fennoscandian Ice Sheet. The cores were radiocarbon dated and analysed for loss on ignition and diatoms. The isolation thresholds of the basins were determined using LiDAR data. The results provide evidence for the initiation of the first Littorina Sea transgression in this area at 8.5 thousand calibrated years before present (cal. ka BP). A relative sea level rise by ∼7 m a.s.l. is recorded between 8.0 and 7.5 cal. ka BP with a highstand at ∼22 m a.s.l. between 7.5 and 6.2 cal. ka BP. These phases coincide with the second and third Littorina Sea transgressions, respectively, in the Blekinge area, southern Sweden and are consistent with the final deglaciation of North America. After 6.2 cal. ka BP, the relative sea level dropped below 22 m a.s.l., and remained at ∼20 m a.s.l. until 4.6 cal. ka BP coinciding with the fourth Littorina Sea transgression in Blekinge. From 4.6 to 4.2 cal. ka BP, the shore displacement shows a regression rate of 10 mm a⁻¹ followed by a slowdown with a mean value of 4.6 mm a⁻¹ until 1.6 cal. ka BP, when the relative sea level dropped below 3.3 m a.s.l. The Middle to Late Holocene highstand and other periods of minor sea level transgressions and/or higher salinity between 6.2 and 1.7 cal. ka BP are attributed to a combination of warmer climate and higher inflow of saline waters in the southern Baltic Sea due to stronger westerlies, caused by variations in the North Atlantic atmospheric patterns.     

Debris flow overflowing flexible barrier: physical process and drag load characteristics

Landslides - The multiple-barrier mitigation strategy in the debris-flow source area is an effective approach to inhibit debris-flow entrainment and scale amplification along the flow path....     

Hybrid continuum–discrete simulation of granular impact dynamics

Acta Geotechnica - Granular impact—the dynamic intrusion of solid objects into granular media—is widespread across scientific and engineering applications including geotechnics....     

Photochemical characteristics of high and low ozone episodes observed in the Taehwa Forest observatory (TFO) in June 2011 near Seoul South Korea

We present a comprehensive discussion on what cause high ozone episodes at a suburban photochemical observation site of the Seoul Metropolitan Area (population ～23 million). The observational site, Taehwa Research Forest (TRF), is situated ～30 km from the center of Seoul. In June 2011, we observed two very distinctive ozone periods-high ozone (peak up to 120 ppbv) and low ozone (peak up to 60 ppbv) in the mid and early month, respectively. The trace gas measurement dataset, especially CO and NO _X clearly indicate that less anthropogenic influences during the high ozone period. Volatile organic compound (VOC) measurement results show that at the observational site, biogenic VOCs (mostly isoprene) contribute most of chemical reactivity towards OH, although toluene from anthropogenic activities was observed in higher concentrations. Back-trajectory analysis indicates that air-masses from the forest part of Korea Peninsula were dominant influences during the high ozone episode event. On the other hand, Aged air masses from China were the dominant influence during the low ozone episode event. Model calculations conducted using the University of Washington Chemical Mechanism (UWCM) box model, also consistently show that BVOC, especially isoprene photochemistry, can be the significantly contribution to local ozone formation in the given photochemical environments of TRF. These research results strongly suggest that ozone control strategy in the Eastern Asian megacities, mostly situated in surrounding forest areas should be based on the comprehensive scientific understanding in BVOC photochemistry and interplays between anthropogenic and biogenic interactions.