Bioattenuation in groundwater impacted by landfill leachate traced with δ13C

The impact on groundwater imparted by the infiltration of high dissolved organic carbon (DOC) leachate from capped, unlined landfills can be attenuated by biogeochemical reactions beyond the waste source, although such reactive loss in the aquifer is difficult to distinguish from conservative advective dispersion. Compound-specific measurement of δ(13)C in carbon species, including CH(4), dissolved inorganic carbon (DIC), and the major DOC compounds (acetate, humic acid, and fulvic acid) provides a constraint in this assessment that can assist in exercises of modeling and prediction of leachate transport. The Trail Road municipal landfill near Ottawa, Ontario, Canada, hosts an unlined sector which produces a highly enriched leachate (DOC >4500 mg/L) that provides a good site to examine reactive attenuation within the receptor aquifer. Acetate, a sentinel component of leachate DOC (~1000 mg C/L), is absent in impacted groundwater. Mass balance calculations together with reaction modeling suggest continued acetate fermentation with calcite control on DIC and δ(13)C(DIC) evolution. In groundwater within 50 m of the landfill, methane concentrations are elevated (~10 mg/L), consistent with acetate fermentation, whereas δ(13)C(CH4) measurements in deeper groundwater range down to -51‰ compared with -60‰ in the landfill demonstrating oxidative loss. DOC in the deep aquifer is remarkably depleted to values less than -40‰ suggesting methanotrophic bacteria selectively consume isotopically light CH(4) to fix carbon. Continued reaction of leachate DOC in groundwater is demonstrated by evolution away from conservative mixing lines on diagrams of δ(13)C vs. concentrations of DIC and DOC.     

Origin of magmatic sulfides in a Proterozoic island arc—an example from the Portneuf–Mauricie Domain,Grenville Province,Canada

The Portneuf–Mauricie Domain (PMD), located in the south-central part of the Grenville province, contains Mesoproterozoic Ni–Cu ± platinum-group element (PGE) prospects hosted in a variety of plutonic intrusions (layered, with simple structures, or zoned) and emplaced in a mature island arc setting. A two-stage model is envisaged to explain the formation of magmatic sulfides. An early loss of a small amount of sulfides in the conduits of primitive, hydrous mantle-derived melts under high fO₂, resulted in depletion of the magmas in chalcophile and precious metals (Cu/Pd ratios vary from initial mantle values up to 1.6 × 10⁶). Then, nearer the mineralized zones, the magmas interacted with sulfide-bearing country rocks, resulting in felsification of the magmas, assimilation of crustal sulfur (δ ³⁴S values up to +5.5‰), and the formation of an immiscible sulfide liquid. Liquid-sulfide formation was followed by variable interactions between the silicate and sulfide magmas, which were responsible for the enrichment of sulfides in Ni, Cu, and, locally, PGE. Indeed, low R factors are found for prospects hosted in intrusions with a simple internal structure and in layered intrusions whereas high R factors are found for prospects hosted in zoned intrusions. Finally, sulfide melt may have been partly incorporated into later pulses of magma and injected into shallow magma chambers to form the PMD prospects. The PMD prospects share common characteristics with other well-known deposits (Aguablanca, Vammala, Stormyrplunen, and deposits in Alaskan/Ural-type intrusions), attesting to the Ni, Cu, and PGE potential of deposits associated with subduction-zone settings.     

New constraints on UHT metamorphism in the Eastern Ghats Province through the application of phase equilibria modelling and in situ geochronology

High Mg–Al granulites from the Sunki locality in the central portion of the Eastern Ghats Province record evidence for the high-temperature peak and retrograde evolution. Peak metamorphic phase assemblages from two samples are garnet + orthopyroxene + quartz + ilmenite + melt and orthopyroxene + spinel + sillimanite + melt, respectively. Isochemical phase diagrams (pseudosections) based on bulk rock compositions calculated in the chemical system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) and Al contents in orthopyroxene indicate peak UHT metamorphic conditions in excess of 960 °C and 9.7 kbar. Microstructures and the presence of cordierite interpreted to record the post-peak evolution show that the rocks underwent decompression and minor cooling from conditions of peak UHT metamorphism to conditions of ~ 900 °C at ~ 7.5 kbar. In situ U–Pb isotope analyses of monazite associated with garnet and cordierite using the Sensitive High Resolution Ion Microprobe (SHRIMP) yield a weighted mean ²⁰⁷Pb/²³⁵U age of ca. 980 Ma, which is interpreted to broadly constrain the timing of high-temperature monazite growth during decompression and melt crystallization at ~ 900–890 °C and 7.5 kbar. However, the range of ²⁰⁷Pb/²³⁵U monazite ages (from ca. 1014 Ma to 959 Ma for one sample and ca. 1043 Ma to 922 Ma for the second sample) suggest protracted monazite growth during the high-temperature retrograde evolution, and possibly diffusive lead loss during slow cooling after decompression. The results of the integrated petrologic and geochronologic approach presented here are inconsistent with a long time gap between peak conditions and the formation of cordierite-bearing assemblages at lower pressure, as proposed in previous studies, but are consistent with a simple evolution of a UHT peak followed by decompression and cooling.     

Distinguishing lower and upper crustal processes in magmas erupted during the buildup to the 7.7 ka climactic eruption of Mount Mazama, Crater Lake, Oregon, using 238U–230Th disequilibria

Uranium-series isotope ratios determined for 35 volcanic rocks and 4 glass separates erupted from ~36 to 4.8 ka at Mt. Mazama, Crater Lake, Oregon, identify both ²³⁰Th-excess and ²³⁸U-excess components. U–Th isotope compositions cover a wide range, exceeding those previously measured for the Cascade arc. Age-corrected (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) activity ratios range from 1.113 to 1.464 and from 0.878 to 1.572 (44.4 % ²³⁰Th-excess to 8.8 % ²³⁸U-excess), respectively. The most distinctive aspect of the data set is the contrast in U–Th isotope ratios between low and high Sr (LSr, HSr) components that have been previously identified in products of the 7.7 ka caldera-forming climactic eruption and preclimactic rhyodacite lavas. The LSr component exclusively contains ²³⁸U-excess, but the HSr component, as well as more primitive lavas, are marked by ²³⁰Th-excess. ²³⁰Th-excesses such as those recorded at Mt. Mazama are commonly observed in the Cascades. Melting models suggest that high ²³⁰Th-excesses observed in the more primitive lavas evolved through mixing of a mantle melt with a partial melt of a mafic lower crustal composition that contained garnet in the residuum that was produced through dehydration melting of amphibolite that was initially garnet free. Dehydration melting in the lower crust offers a solution to the “hot-slab paradox” of the Cascades, where low volatile contents are predicted due to high slab temperatures, yet higher water contents than expected have been documented in erupted lavas. The ²³⁸U-excess observed at Mt. Mazama is rare in Cascade lavas, but occurs in more than half of the samples analyzed in this study. Traditionally, ²³⁸U-excess in arc magmas is interpreted to reflect slab fluid fluxing. Indeed, ²³⁸U-excess in arcs is common and likely masks ²³⁰Th-excess resulting from lower crustal interaction. Isotopic and trace element data, however, suggest a relatively minor role for slab fluid fluxing in the Cascades. We propose that ²³⁸U-excess reflects melting and assimilation of young, hydrothermally altered upper crust. The processes related to generating ²³⁸U-excess are likely important features at Mt. Mazama that accompanied development of a large-scale silicic magma chamber that led to the caldera-forming eruption.     

Timing of advance and basal condition of the Laurentide Ice Sheet during the last glacial maximum in the Richardson Mountains,NWT

This study presents new ages for the northwest section of the Laurentide Ice Sheet (LIS) glacial chronology from material recovered from two retrogressive thaw slumps exposed in the Richardson Mountains, Northwest Territories, Canada. One study site, located at the maximum glacial limit of the LIS in the Richardson Mountains, had calcite concretions recovered from aufeis buried by glacial till that were dated by U/Th disequilibrium to 18,500 cal yr BP. The second site, located on the Peel Plateau to the east yielded a fossil horse (Equus) mandible that was radiocarbon dated to ca. 19,700 cal yr BP. These ages indicate that the Peel Plateau on the eastern flanks of the Richardson Mountains was glaciated only after 18,500 cal yr BP, which is later than previous models for the global last glacial maximum (LGM). As the LIS retreated the Peel Plateau around 15,000 cal yr BP, following the age of the Tutsieta phase, we conclude that the presence of the northwestern margin of the LIS at its maximum limit was a very short event in the western Canadian Arctic.     

Isotope Constraints on the Aquatic Carbon Budget: Langat Watershed,Malaysia

Langat River drains a tropical watershed in the southwest of the Malaysian Peninsula. The watershed is heavily urbanized in its downstream portion. Water samples were collected from May 2010 to December 2011, at three localities along the main stem river, 1 location at its Semenyih tributary and from an upstream groundwater source. Concentration and δ¹³C data of riverine DIC and DOC indicate the dominance of C3 plant-derived material as the primary source of carbon, with δ¹³C_DIC values enriched in ¹³C relative to that of the C3 source. This enrichment is likely due to CO₂ outgassing, as calculated concentrations of riverine CO₂ are significantly higher than ambient atmospheric values, with methanogenic activity a theoretically possible contributing factor, particularly at the upstream location. The Langat River therefore acts as a net source of CO₂, with a total sub-basin flux of 19.7 × 10³ t C year^?1. This is comparable to the sum of riverine DOC, DIC and POC loss rates from the sub-basin, calculated as 24.5 × 10³ t C year^?1, and highlights the significance of CO₂ evasion from water bodies to the atmosphere for balancing the budget of the terrestrial carbon cycle. The DIC and DOC concentration and δ¹³C data also suggests that in the more urbanized downriver areas, much of the organic carbon input may be anthropogenicaly derived due to ubiquity of sewage treatment plants and landfill sites. Such human-induced perturbations to riverine carbon cycling should be taken into account in future studies of urbanized watersheds.     

The use of reference models from a priori data to guide 2D inversion of electrical resistivity tomography data

Clay-rich till plains cover much of the UK. Such sites are attractive locations for landfills, since clay aquitards lower the risk of landfill leachate entering groundwater. However, such tills often contain sand and gravel bodies that can act as leachate flow routes. Such bodies may not be detected by conventional site investigation techniques such as drilling boreholes and trial pitting. A method of guided inversion, where a priori data are used to construct structural reference models for use in inverting electrical resistivity tomography data, was proposed as a tool to improve the detection of sand and gravel bodies within clay-rich till sequences.
Following a successful 2D guided inversion synthetic modelling study, a field study was undertaken. Wenner 2D electrical resistivity tomography lines, resistivity cone penetrometry bores and electromagnetic induction ground resistivity data were collected over a site on the East Yorkshire coast, England, where sand and gravel lenses were known to exist from cliff exposures. A number of equally valid geoelectrical models were constructed using the electromagnetic and resistivity cone data. These were used as structural reference models in the inversion of the resistivity tomography data. Blind inversion using an homogenous reference model was also carried out for comparison.
It was shown for the first time that the best solution model produced by 2D inversion of one data set with a range of structural reference models could be determined by using the l ₂ model misfit between the solution models and associated reference models (reference misfit) as a proxy for the l ₂ misfit between the solution models and the synthetic model or 'best-guess' geoelectrical model (true misfit). The 2D methodology developed here is applicable in clay-rich till plains containing sand and gravel bodies throughout the UK.     

Evaluating Quaternary dating methods: Radiocarbon,U-series,luminescence, and amino acid racemization dates of a late Pleistocene emu egg

A whole emu egg, with infilling sediment believed to be coeval with egg laying and burial, was found in late Pleistocene lunette sediments near Lake Eyre, central Australia. The stratigraphic context and initial amino acid racemization (AAR) results suggested an age between 25 ka and 35 ka, ideal for a multiple cross-dating comparison. The sediment infilling the egg provided material for luminescence dating that minimized problems of association. Age estimations from AAR, ¹⁴C and U series methods were obtained from the eggshell and optically stimulated luminescence (OSL) of the infilling sediment. All methods agreed within their respective dating uncertainties confirming the utility of all four methods. They indicate an age for the emu egg of 31.24 ± 0.34 ka.     

Times of sand: Sedimentary history and archaeology at the Sigatoka Dunes,Fiji

The orthodox archaeological sequence at the Sigatoka Dunes site (VL 16/1) in Fiji proposes three phases of occupation spanning Fijian prehistory, each associated with a period of dune stability. It has been taken as the standard model of Fijian prehistory for more than 30 years. Recently, however, it has been argued that there is no stratigraphic support for three discrete levels and that the occupation history was fragmented, complex, and continuous within a volatile dune system. We present new data, from optical and radiocarbon dating, to argue that a three‐phase model, although somewhat more complex in detail, remains the most robust interpretation of site history. The longest stable phase (Level 2) began 2500–2300 cal yr B.P. and is possibly associated with relatively low ENSO frequency. Substantial sand dune accumulation began after ˜1300 cal yr B.P. © 2006 Wiley Periodicals, Inc.