Pore Water Characteristics Following a Release of Neat Ethanol onto Pre-existing NAPL

Neat ethanol (75.7 L) was released into the upper capillary zone in a continuous-flow, sand-packed aquifer tank (8.2 m³) with an average seepage velocity of 0.75 m/day. This model aquifer system contained a residual nonaqueous phase liquid (NAPL) that extended from the capillary zone to 10 cm below the water table. Maximum aqueous concentrations of ethanol were 20% v/v in the capillary zone and 0.08% in the saturated zone at 25 and 30 cm downgradient from the emplaced NAPL source, respectively. A bench-scale release experiment was also conducted for a similar size spill (scaled to the plan area). The concentrations of ethanol in ground water for both the bench- and pilot-scale experiments were consistent with advective–dispersive limited mass transfer from the capillary to the saturated zone. Concentrations of monoaromatic hydrocarbons and isooctane increased in the pore water of the capillary zone as a result of both redistribution of residual NAPL (confirmed by visualization) and enhanced hydrocarbon dissolution due to the cosolvent effect exerted by ethanol. In the tank experiment, higher hydrocarbon concentrations in ground water were also attributed to decreased hydrocarbon biodegradation activity caused by preferential microbial utilization of ethanol and the resulting depletion of oxygen. These results infer that spills of highly concentrated ethanol will be largely confined to the capillary zone due to its buoyancy, and ethanol concentrations in near-source zone ground water will be controlled by mass transfer limitations and hydrologic conditions. Furthermore, highly concentrated ethanol releases onto pre-existing NAPL will likely exacerbate impacts to ground water, due to NAPL mobilization and dissolution, and decreased bioattenuation of hydrocarbons.     

Evaluation of spatially clustered ordnance when using compliance sampling surveys after clean-up at military training sites

After site clean-up teams have removed all of what they believe to be UXO within a specific impact area, statistical compliance sampling is a possible method for verifying with a specified probability that this area has been cleaned to specifications. Schilling [J Qual Technol 10(2):47–51, 1978, Acceptance sampling in quality control. Marcel Dekker, Inc., New York, 1982] developed a compliance sampling methodology based on the hypergeometric distribution. Bowen and Bennett (1987) also use compliance sampling where they provide an approximation for estimating the number of samples (n) required to state with desired probability that the entire population of sample units (N, where n < N) are in compliance with cleanup goals. This article describes two methods (anomaly and transect) for applying the Schilling [J Qual Technol 10(2):47–51, 1978, Acceptance sampling in quality control. Marcel Dekker, Inc., New York, 1982] compliance sampling method to military training sites. After describing these methods, a simulation study is presented which demonstrates the performance of transect compliance sampling calculations based on varied degrees of clustered UXO within a specific impact area and different types of sampling routines.     

Data reporting norms for 40Ar/39Ar geochronology

Data reported in ⁴⁰Ar/³⁹Ar geochronology studies are commonly insufficient to allow computation of ages. This deficiency renders it difficult to compare ages based on different standards or constants, and often hinders critical evaluation of the results. Herein are presented an enumeration of the data that should be reported in all ⁴⁰Ar/³⁹Ar studies, including a discussion in support of these requirements. The minimum required data are identified and distinguished from parameters that are useful but may be derived from them by calculation. Finally, recommendations are made for metadata needed to document age calculations (e.g., from age spectrum or isochron analyses).     

Geochemistry and geodynamics of a Late Cretaceous bimodal volcanic association from the southern part of the Pannonian Basin in Slavonija (Northern Croatia)

Summary ?In this paper we present petrological and geochemical information on a bimodal basalt-rhyolite suite associated with A-type granites of Late Cretaceous age from the South Pannonian Basin in Slavonija (Croatia). Basalts and alkali-feldspar rhyolites, associated in some places with ignimbrites, occur in volcanic bodies that are interlayered with pyroclastic and fossiliferous Upper Cretaceus sedimentary rocks. The petrology and geochemistry of the basalts and alkali-feldspar rhyolites are constrained by microprobe analyses, major and trace element analyses including REE, and radiogenic and stable isotope data. Basalts that are mostly transformed into metabasalts (mainly spilites), are alkalic to subalkalic and their geochemical signatures, particularly trace element and REE patterns, are similar to recent back-arc basalts. Alkali-feldspar rhyolites have similar geochemical features to the associated cogenetic A-type granites, as shown by their large variation of Na₂O and K₂O (total 8–9%), very low MgO and CaO, and very high Zr contents ranging between 710 and 149 ppm. Geochemical data indicate an amphibole lherzolite source within a metasomatized upper mantle wedge, with the influence of upper mantle diapir with MORB signatures and continental crust contamination. Sr incorporated in the primary basalt melt had an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7039 indicating an upper mantle origin, whereas the ⁸⁷Sr/⁸⁶Sr ratio for the alkali-feldspar rhyolites and associated A-type granites is 0.7073 indicating an apparent continental crust origin. However, some other geochemical data favour the idea that they might have mainly originated by fractionation of primary mafic melt coupled with contamination of continental crust. Only one rhyolite sample appears to be the product of melting of continental crust. Geological and geodynamic data indicate that the basalt-rhyolite association was probably related to Alpine subduction processes in the Dinaridic Tethys which can be correlated with recent back-arc basins. The difference in geological and isotope ages between the bimodal basalt-rhyolite volcanism with A-type granite plutonism (72 Ma) and the final synkinematic S-type granite plutonism (48 Ma) can be taken as a lifetime of the presumed BARB system of the Dinaridic Tethys. Remnants of this presumed subduction zone can be traced for 300 km along the surrounding northernmost Dinarides.

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Zusammenfassung ?Zur Geochemie und Geodynamik einer sp?tkretazischen bimodalen Vulkanit-Assoziation aus dem südlichen Pannonischen Becken, Slavoníen (Nordkroatien) In dieser Arbeit pr?sentieren wir petrologische und geochemische Daten einer bimodalen Basalt – Rhyolithsuite aus dem südlichen Pannonischen Becken in Slavonien (Kroatien), die mit A-Typ Graniten kretazischen Alters assoziiert ist. Die Basalte und Alkalifeldspat-Rhyolithe – sie sind stellenweise mit Ignimbriten vergesellschaftet – treten in vulkanischen K?rpern auf, die mit pyroklastischen und fossilführenden Sedimentgesteinen der Oberen Kreide wechsellagern. Die Petrologie und Geochemie der Basalte und Alkalifeldspat-Rhyolithe wird durch Mikrosondenuntersuchungen, Haupt- und Spurenelementgeochemie, inklusive der SEE, sowie durch radiogene und stabile Isotope eingegrenzt. Die Basalte, die gro?teils in Metabasalte (haupts?chlich Spilite) umgewandelt wurden, sind alkalisch bis subalkalisch und ihre geochemischen Charakteristika, haupts?chlich die Spurenelement- und die SEE- Patterns, sind ?hnlich rezenten Back-Arc Basalten. Die Alkalifeldspat-Rhyolithe zeigen geochemische Auml;hnlichkeiten mit den assoziierten cogenetischen A-Typ Graniten, was sich in der gro?en Variation der Na₂O und K₂O-Gehalte (in Summe 8–9%), in niedrigen MgO- und CaO- und in sehr hohen Zr- Gehalten, die zwischen 149 und 710 ppm liegen, widerspiegelt. Die geochemischen Daten zeigen eine Amphibolit-Lherzolithquelle innerhalb eines metasomatisierten Mantelkeils mit Einflüssen eines Diapirs des oberen Mantels mit MORB-Signatur und kontinentaler Krustenkontamination an. Sr der prim?ren Basalte hatte ein ⁸⁷Sr/⁸⁶Sr Initial von 0.7039, was eine Herkunft aus dem oberen Mantel anzeigt. Das ⁸⁷/⁸⁶Sr Verh?ltnis der Alkalifeldspat-Rhyolithe und der assoziierten A-Typ Granite von 0.7073 weist auf eine krustale Herkunft hin. Andere geochemische Daten allerdings favorisieren die Idee, da? diese durch Fraktionierung prim?rer mafischer Schmelzen, gekoppelt mit Kontamination durch kontinentale Kruste, entstanden. Nur eine Rhyolithprobe scheint ein tats?chliches Aufschmelzungsprodukt der kontinentalen Kruste zu sein. Die geologischen und geodynamischen Daten belegen, dass die Basalt–Rhyolithabfolge wahrscheinlich mit der alpidischen Subduktion in der Thetys der Dinariden, die mit rezenten Back-Arc Becken korreliert werden kann, in Beziehung zu setzen ist. Die Unterschiede zwischen den geologischen und Isotopenaltern des bimodalen Vulkanismus, mit A-Typ Granit-Plutonismus (72 Ma) und finalem synkinematischen S-Typ Granit-Plutonismus (48 Ma), repr?sentiert sehr wahrscheinlich die Dauer des vermuteten BARB Systems in der Thetys der Dinariden. Relikte der vermuteten Subduktionszone lassen sich über 300 km entlang der umgebenden n?rdlichsten Dinariden verfolgen.

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Received March 7, 1997;/revised version accepted May 18, 1999     

Evidence for the enhanced lability of dissolved organic matter following permafrost slope disturbance in the Canadian High Arctic

Arctic landscapes are believed to be highly sensitive to climate change and accelerated disturbance of permafrost is expected to significantly impact the rate of carbon cycling. While half the global soil organic matter (SOM) is estimated to reside in Arctic soils, projected warmer temperatures and permafrost disturbance will release much of this SOM into waterways in the form of dissolved organic matter (DOM). The spring thaw and subsequent flushing of soils releases the highest contributions of DOM annually but has historically been undersampled due to the difficulties of sampling during this period. In this study, passive samplers were placed throughout paired High Arctic watersheds during the duration of the 2008 spring flush in Nunavut, Canada. The watersheds are very similar with the exception of widespread active layer detachments (ALDs) that occurred within one of the catchments during a period of elevated temperatures in the summer of 2007. DOM samples were analyzed for structural and spectral characteristics via nuclear magnetic resonance (NMR) and fluorescence spectroscopy as well as vulnerability to degradation with simulated solar exposure. Lignin-derived phenols were further assessed utilizing copper(II) oxide (CuO) oxidation and gas chromatography/mass spectrometry (GC/MS). The samples were found to have very low dissolved lignin phenol content (∼0.07% of DOC) and appear to originate from primarily non-woody angiosperm vegetation. The acid/aldehyde ratios for dissolved vanillyl phenols were found to be high (up to 3.6), indicating the presence of highly oxidized lignin. Differences between DOM released from the ALD vs. the undisturbed watershed suggest that these shallow detachment slides have significantly impacted the quality of Arctic DOM. Although material released from the disturbed catchment was found to be highly oxidized, DOM in the lake into which this catchment drained had chemical characteristics indicating high contributions from microbial and/or primary productivity. The resulting pool of dissolved carbon within the lake appears to be more biologically- and photochemically-labile than material from the undisturbed system. These disturbances may have implications for projected climate warming; sustained elevated temperatures would likely perpetuate widespread ALDs and further affect carbon cycling in this environment.     

Emplacement age and thermal footprint of the diamondiferous Ellendale E9 lamproite pipe, Western Australia

The diamondiferous Ellendale 9 (E9) pipe is a funnel-shaped maar-diatreme volcano consisting of inward-dipping tuff sequences intruded by lamproite plugs and dykes. The host rocks for the E9 pipe are Permian sandstones. The multiple lithological contacts exposed within the mined maar volcano provide a natural laboratory in which to study the effect of volcanic processes on U–Th–Pb–He systematics. Zircon from the regional sandstone and E9 lamproite display a bimodal distribution of ages on (U–Th)/He–U/Pb plots. The zircon U/Pb ages for the E9 pipe (n?=?52) range from 440 to 2,725 Ma, while the cluster of (U–Th)/He ages for the lamproite dyke zircon indicate that dyke emplacement occurred at 20.6?±?2.8 Ma, concordant with a maximum emplacement age of about ≤22 Ma from phlogopite ⁴⁰Ar/³⁹Ar. These ages indicate a xenocrystic origin for the zircon entrained in the E9 dyke. The U/Pb ages of detrital zircon from the regional sandstone host (373–3,248 Ma; n?=?41) are indistinguishable from those of the lamproite zircon xenocrysts, whereas the detrital zircon in the host sandstone yield (U–Th)/He ages from 260 to 1,500 Ma. A thermochronology traverse across the E9 lamproite dyke reveals that the zircon (U–Th)/He ages in the host sandstone have not been significantly thermally reset during dyke emplacement, even at the contact. The capability of the zircon (U–Th)/He method to distinguish deep, mantle source lithologies from upper crustal source lithologies could be used in geochemical exploration for diamonds. Pre-screening of detrital samples using etching and helium assay methods will improve the efficiency and decrease the cost of greenfields exploration.     

Consequences of change and variability in sea ice on marine ecosystem and biogeochemical processes during the 2007–2008 Canadian International Polar Year program

Change and variability in the timing and magnitude of sea ice geophysical and thermodynamic state have consequences on many aspects of the arctic marine system. The changes in both the geophysical and thermodynamic state, and in particular the timing of the development of these states, have consequences throughout the marine system. In this paper we review the ??consequences?? of change in sea ice state on primary productivity, marine mammal habitats, and sea ice as a medium for storage and transport of contaminants and carbon exchange across the ocean-sea-ice-atmosphere interface based upon results from the International Polar Year. Pertinent results include: 1) conditions along ice edges can bring deep nutrient-rich ??pacific?? waters into nutrient-poor surface waters along the arctic coast, affecting local food webs; 2) both sea ice thermodynamic and dynamic processes ultimately affect ringed seal/polar bear habitats by controlling the timing, location and amount of surface deformation required for ringed seal and polar bear preferred habitat 3) the ice edges bordering open waters of flaw leads are areas of high biological production and are observed to be important beluga habitat. 4) exchange of climate-active gases, including CO₂, is extremely active in sea ice environments, and the overall question of whether the Arctic Ocean is (or will be) a source or sink for CO₂ will be dependent on the balance of competing climate-change feedbacks.     

The policy relevance of global environmental change research

Many scientists are striving to identify and promote the policy implications of their global change research. Much basic research on global environmental change cannot advance policy directly, but new projects can determine the relevance of their research to decision makers and build policy-relevant products into the work. Similarly, many ongoing projects can alter or add to the present science design to make the research policy relevant. Thus, this paper shows scientists working on global change how to make their research policy relevant. It demonstrates how research on physical global change relates to human dimensions studies and integrated assessments. It also presents an example of how policy relevance can be fit retroactively into a global change project (in this case, SRBEX—the Susquehanna River Basin Experiment) and how that addition can enhance the project's status and science. The paper concludes that policy relevance is desirable from social and scientific perspectives.     

The Taylor Creek Rhyolite of New Mexico: a rapidly emplaced field of lava domes and flows

The Tertiary Taylor Creek Rhyolite of southwest New Mexico comprises at least 20 lava domes and flows. Each of the lavas was erupted from its own vent, and the vents are distributed throughout a 20 km by 50 km area. The volume of the rhyolite and genetically associated pyroclastic deposits is at least 100 km³ (denserock equivalent). The rhyolite contains 15%–35% quartz, sanidine, plagioclase, ±biotite, ±hornblende phenocrysts. Quartz and sanidine account for about 98% of the phenocrysts and are present in roughly equal amounts. With rare exceptions, the groundmass consists of intergrowths of fine-grained silica and alkali feldspar. Whole-rock major-element composition varies little, and the rhyolite is metaluminous to weakly peraluminous; mean SiO₂ content is about 77.5±0.3%. Similarly, major-element compositions of the two feldsparphenocryst species also are nearly constant. However, whole-rock concentrations of some trace-elements vary as much as several hundred percent. Initial radiometric age determinations, all K–Ar and fission track, suggest that the rhyolite lava field grew during a period of at least 2 m.y. Subsequent ⁴⁰Ar/³⁹Ar ages indicate that the period of growth was no more than 100 000 years. The time-space-composition relations thus suggest that the Taylor Creek Rhyolite was erupted from a single magma reservoir whose average width was at least 30 km, comparable in size to several penecontemporaneous nearby calderas. However, this rhyolite apparently is not related to a caldera structure. Possibly, the Taylor Creek Phyolite magma body never became sufficiently volatile rich to produce a large-volume pyroclastic eruption and associated caldera collapse, but instead leaked repeatedly to feed many relatively small domes and flows.The new ⁴⁰Ar/³⁹Ar ages do not resolve preexisting unknown relative-age relations among the domes and flows of the lava field. Nonetheless, the indicated geologically brief period during which Taylor Creek Rhyolite magma was erupted imposes useful constraints for future evaluation of possible models for petrogenesis and the origin of trace-element characteristics of the system.