Controls on dissolved inorganic carbon and δC in cave waters from DeSoto Caverns: Implications for speleothem δC assessments

Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ¹³C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ¹³C_DIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ¹³C_DIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ¹³C_DIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ¹³C_DIC = −2.49[DIC] + 0.64, r² = 0.84). A shallow pool fed by multiple drips shows a bimodal δ¹³C_DIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO₂ fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ¹³C_DIC variability. Measured values of high [DIC] and low δ¹³C_DIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ¹³C_DIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO₂ and precipitated CaCO₃(1000lnα_{[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2}) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of ¹⁴C mass balance and paired ¹⁴C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from ¹⁴C-dead dolomite cap while the remainder of ∼77% is derived from ¹⁴C-live biomass. δ¹³C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ¹³C values calculated using the shallow pool summer/early fall data thus confirming the δ¹³C seasonality in both drips and coeval aragonite. δ¹³C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ¹³C records of stalagmites at DeSoto Caverns with resolving power >10⁻¹ year will likely carry the imprints of drip annual means that record climate-driven δ¹³C seasonal biases.     

Mobilization of actinides by dissolved organic compounds at the Nevada Test Site

The effect of dissolved organic matter (DOM) on Am(III), Pu(IV), Np(V), and U(VI) sorption was investigated with natural water (pH ∼8) and zeolitized tuff samples collected from the Rainier Mesa tunnel system, Nevada Test Site, where the USA detonated underground nuclear tests prior to 1992. Perched vadose zone water at Rainier Mesa has high levels of DOM as a result of microbial degradation of mining debris (diesel, wood, etc.). The Am and Pu sorption K_ds were up to two orders of magnitude lower in water with high DOM (15-19 mg C/L) compared to the same water with DOM removed (<0.4 mg C/L) or in naturally low DOM (0.2 mg C/L) groundwater. In contrast, K_ds of Np and U were less affected by DOM at these solution conditions. Uranium sorption decreased as a result of high dissolved inorganic C (DIC) resulting from microbial degradation of DOM. Thermodynamic model predictions, based on actinide-humic acid stability constants available in the literature, are in general agreement with measured K_d data, correctly predicting the effects of DIC and DOM on actinide retardation. This agreement is encouraging to future modeling efforts and suggests that effects of DOM and DIC can be incorporated into reactive transport modeling predictions. The Am and Pu transport rates in Rainier Mesa tunnel waters will be substantially faster as a result of the elevated DOM levels. Low diffusion rates of actinide-DOM macromolecular complexes may focus Pu and Am transport into fractures and minimize retardation via matrix diffusion. The resulting transport behavior will affect actinide distribution patterns and associated risk estimates.     

What happened to surface temperature with sunspot activity in the past 130 years?

Based on composite analysis using categories of solar inactivity and activity, the responses of surface temperature to different categorized solar activity and a plausible mechanism have been discussed. The results show the increasing solar sunspot activity during solar cycles 13 to 24 (1880–2010) and it seemed to make a positive contribution to rising global temperature. However, the sunspots were fewer in number, if we focused on the most recent 60 years (1950–2010), and the decreasing solar activity did not contribute to a cooler Earth. This result indicates that the connection between sunspots and the Earth’s climate is sensitive to the study period. An extreme analysis was performed in an attempt to gain a better understanding of solar impacts. The extreme top 10 composite analysis demonstrated that the surface temperature response to solar activity is spatially different and is highly sensitive to El Niño–Southern Oscillation (ENSO) events. The most sensitive areas in the Pacific sector revealed a significant difference between including and excluding ENSO years. During the solar inactive years, the tropical eastern Pacific was observed as a weak El Niño-like (strong La Niña-like) pattern in the composite including (excluding) ENSO events. Another interesting feature is the strong similarity in the composites which include or exclude ENSO events during the sunspot active years, but it differs from the La Niña-like pattern observed in previous studies. The bottom-up mechanism associated with the response of the surface dynamical circulation and the heat balance when compared to the total solar irradiance forcing partially explains the connection.     

Spectroscopic Observations of the 2011 Draconids Meteor Shower

Some past October Draconid shower meteoroids fell apart in a spray of fragments at the end of their trajectory before slowing down, from which it was concluded that these were among the most fragile meteoroids known. In those instances, the dust could not be reliably traced to a particular return of the parent comet 21P/Giaconini-Zinner. On October 8th, 2011, Earth was predicted to transverse the 1900 A.D. dust ejecta of the comet. In 1900, the comet’s perihelion distance first moved significantly inwards to the Sun and ejection conditions could have been unusual. An airborne observing campaign was organized, with several teams contributing imaging and spectrographic cameras to study the manner in which these meteoroids released the volatile element sodium during the ablation process in the Earth’s atmosphere. IMCCE, ESA, and the SETI Institute contributed spectrographic cameras based on low-light WATEC 902H2 Ultimate, low-light LCC1, and GenII XX1332 image intensified cameras. An outburst was observed, much as predicted. Despite a lack of bright meteors, a total of 15 Draconid spectra were recorded. All show evidence of an early release of sodium. The loss of sodium was observed to coincide with the formation of a distinct wake of fragments. The observations show that 21P/Giacobini-Zinner ejected fragile meteoroids during the return in 1900. Those grains may have lost some sodium even before impacting Earth.     

The fossil vertebrates from Lano (Basque Country, Spain); new evidence on the composition and affinities of the Late Cretaceous continental faunas of Europe

A newly discovered fossil locality at Lano (Basque Country) has yielded a vertebrate assemblage of probably Maastrichtian age comprising fishes, amphibians, reptiles and mammals. It considerably enlarges our knowledge of the Late Cretaceous continental faunas of Europe, hitherto based on a much less complete record. Some taxa are recorded for the first time in Europe, and the fauna also contains the oldest known representatives of some groups (amphisbaenians, salamandrids). The Lan assemblage reveals an original fauna comprising both forms related to Asian and North American groups and elements with Gondwanan affinities.     

Application of kinematic wave theory for predicting flash flood hazards on coupled alluvial fan–piedmont plain landforms

A rainstorm that caused a severe flash flood on the piedmont plain at the toe positions of two alluvial fans located to the west of the Organ Mountains in Dona Ana County, New Mexico, USA, is analysed. The space–time distributions of rainfall are evaluated from the Next Generation Weather Radar (NEXRAD) and overland flow is modelled as kinematic wave. The spatial distribution of rainfall shows a topographic control. The greatest rainfall depth, duration, and intensity occurred at the higher elevation mountain slopes and decreased with decreasing elevation from the alluvial fans to the piedmont plain. The alluvial fan–piedmont plain system is modelled by coupling divergent and rectangular overland flow planes. Explicit finite difference approximations, hybridized with the analytical method of characteristics, are made to the kinematic wave equations to account for the spatial and temporal distribution of the rainfall and variable boundary conditions. Simulation results indicate that sheet‐flow floodwater elevations rise (1) in a nonlinear fashion from the apex to toe positions of the alluvial fans, and (2) near linearly from the toe positions of the alluvial fans onto the piedmont plains with the formation of kinematic shocks near the middle to the upstream end of the plane at times between the initiation of the rainstorm and the time of concentration of the plane. Thus, the maximum flooding occurs at the middle or upstream sections of the piedmont plains regardless of the pattern of space–time variability of rainfall. These results are in agreement with observed geomorphologic features suggesting that piedmont plains are naturally flood‐prone areas. This case study demonstrates that flood hazards on piedmont plains can exceed those on alluvial fans. The models presented in this study suggest that the flood hazard zones on coupled alluvial fan–piedmont plain landforms should be delineated transverse to the flow directions, as opposed to the flood hazard zones with boundaries in the longitudinal direction of the axis of an alluvial fan. Copyright © 2003 John Wiley & Sons, Ltd.     

Using calculated chemical potential relationships to account for replacement of kyanite by symplectite in high pressure granulites

Calculated mineral equilibria are used to account for the formation of sapphirine–plagioclase, spinel–plagioclase and corundum–plagioclase symplectites replacing kyanite in quartz–plagioclase–garnet–kyanite granulite facies gneisses from the Southern Domain of the Athabasca granulite terrane, a segment of the Snowbird tectonic zone in northern Saskatchewan, Canada. Metamorphic conditions of >14 kbar and 800 °C are established for the high pressure, garnet–kyanite assemblage using constraints from P–T pseudosections and Zr‐in‐rutile thermometry. Replacement of kyanite by symplectites reflects the reaction of kyanite with the matrix following near‐isothermal decompression to <10 kbar. The chemical potential gradients developed between the kyanite and the matrix led to diffusion that attempted to flatten the gradients, kyanite persisting as a stable phase while it is consumed by symplectite from its edge. In this local equilibrium model, the mineral and mineral compositional spatial relationships are shown to correspond to paths in μ(Na₂O)–μ(CaO)–μ(K₂O)–μ(FeO)–μ(MgO) in the model chemical system, Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂ (NCKFMAS), with SiO₂ and Al₂O₃ taken to be completely immobile. The values of μ(Na₂O) and μ(CaO) are constrained by fixing P–T conditions and choosing appropriate μ(Na₂O) and μ(CaO) values that correspond to the observed plagioclase compositions. μ(FeO)–μ(MgO) diagrams show the corresponding spatial relationships with kyanite and the symplectite phases. These results demonstrate that the replacement of kyanite by sapphirine–plagioclase and spinel–plagioclase appears to be metastable with respect to replacement by corundum–plagioclase. Replacement by corundum–plagioclase does also occur, apparently overprinting pre‐existing symplectite and also kyanite. Ignoring corundum, the resulting diagrams account for the spatial relationships and compositions observed in the spinel–plagioclase and sapphirine–plagioclase symplectites. They are predicted to occur over both a wide range of P–T conditions (6–11 kbar, 650–850 °C) and plagioclase compositions (X_An = 0.5–0.9). The wide range of P–T conditions that may result in identical spatial and compositional relationships suggests that such reaction textures may be of limited use in accurately quantifying the P–T conditions of retrograde metamorphism.     

Testing of Sydney dimension sandstone for use in the conservation of heritage buildings

This paper deals with the scientific assessment of the physical properties of sandstone used in the conservation of Sydney's historic heritage sandstone buildings. The local Hawkesbury Sandstone has been widely used for all manner of constructions since the early days of the first settlement. In the nineteenth century, dimension sandstone quarries existed all over the Sydney region, and the demand for the stone was great. During this time, a true ‘freestone’ known as ‘yellow block’ sandstone, in which bedding planes were absent, was quarried extensively. This sandstone is also known as a ‘self-colouring’ sandstone, where the rock, although grey when quarried, turns a yellow–brown after a few months exposure to the atmosphere. It can be easily carved and was eminently suitable for the ornate Victorian architecture of the time. There are very few quarries within the Sydney region today capable of producing ‘yellow block’ sandstone. Whenever possible, sandstone from suitable building excavations, particularly on the Pyrmont Peninsula, is used for this work. Conservation work is extremely expensive and the building elements that most need replacement, the overhanging and decorative elements, are usually those that cost the most. It is essential that the most durable replacement stone be selected. Thus, a strict regime of scientific testing is used for any major conservation project, in order to determine the physical properties of possible replacement stone. This is the province of the geologist and involves visual observation in the quarry or excavation, which is a simple, cost-effective means of weeding out poor quality stones, followed by laboratory engineering tests to establish the physical parameters of a sandstone and finally, petrographic analysis. The results of such tests, combined with careful sampling, ensure the best possible quality of replacement material.     

3D seismic technology: the geological 'Hubble'

The proliferation of three‐dimensional (3D) seismic technology is one of the most exciting developments in the Earth Sciences over the past century. 3D reflection seismic data provide interpreters with the ability to map structures and stratigraphic features in 3D detail to a resolution of a few tens of metres over thousands of square kilometres. It is a geological ‘Hubble’, whose resolving power has already yielded some fascinating (and surprising) insights and will continue to provide a major stimulus for research into geological processes and products for many decades to come. Academic and other research institutions have a major role to play in the use of this data by exploiting the enormous volume of geological information contained in 3D seismic surveys. This paper reviews some of the recent advances in basin analysis made using the medium of 3D seismic data, focusing on the fields of structural and sedimentary geology, fluid–rock interactions and igneous geology. It is noted that the increased resolution of the 3D seismic method provided the essential catalyst necessary to stimulate novel observations and discover new geological structures such as mud diapir feeders, km‐long gas blow‐out pipes, giant pockmarks and sandstone intrusions, and to capture the spatial variability of diagenetic fronts. The UKs first impact crater was also discovered using 3D seismic data. The potential for future developments in this field of geophysical interpretation is considerable, and we anticipate that new discoveries will be made in many years to come.     

Evaluation of Vapor Intrusion Risk from Ethylene Dibromide Using the Vertical Screening Distance Approach

Vapor intrusion (VI) occurs when volatile contaminants in the subsurface migrate through the vadose zone into overlying buildings. The 2015 U.S. EPA petroleum VI guidance recommends that additional investigation of the VI risk from gasoline hydrocarbons at the underground storage tank (UST) sites is not necessary where the vertical distance between a building and a vapor source exceeds a recommended vertical screening distance. However, due to the lack of soil-gas data on the attenuation of ethylene dibromide (EDB), additional VI investigations to evaluate VI risk from EDB are recommended at UST sites with leaded gasoline releases containing EDB. We analyzed soil-gas and groundwater concentrations of EDB from eight petroleum UST sites using a new analytical method with soil-gas detection limit <0.16 μg/m³ EDB (VI screening level at the 10⁻⁶ risk level). The analysis included (1) assessing the frequency of EDB detections ≤0.16 μg/m³ at various vertical separation distances and (2) predicting vertical screening distances for EDB using the U.S. EPA PVIScreen model for different soil types in the vadose zone above dissolved-phase and LNAPL sources. Ranges of estimated aerobic biodegradation rate constants for EDB, air exchange rates for residential buildings, and source vapor concentrations for other constituents were combined with conservative estimates of EDB source concentrations as model inputs. Concentrations of EDB in soil-gas indicated that the U.S. EPA recommended vertical screening distances are protective of VI risk from EDB. Conversely, vertical screening distances predicted by modeling were >6 ft (1.8 m) for sites with sand and loam soil above dissolved phase sources and >15 ft (4.6 m) for sites with sand soil above LNAPL sources. This predicted dependence on the vapor source type and soil type in the vadose zone highlights the importance of soil characterization for VI screening at sites with EDB sources.