Fingerprinting fluid source in calcite veins: combining LA-ICP-MS U-Pb calcite dating with trace elements and clumped isotope palaeothermometry

Application of geochemical proxies to vein minerals - particularly calcite - can fingerprint the source of fluids controlling various important geological processes from seismicity to geothermal systems. Determining fluid source, e.g. meteoric, marine, magmatic or metamorphic waters, can be challenging when using only trace elements and stable isotopes as different fluids can have overlapping geochemical characteristics, such as δ18O. In this contribution we show that by combining the recently developed LA-ICP-MS U-Pb calcite geochronometer with stable isotopes (including clumped isotope palaeothermometry) and trace element analysis, the fluid source of veins can be more readily determined. Calcite veins hosted in the Devonian Montrose Volcanic Formation at Lunan Bay in the Midland Valley Terrane of Central Scotland were used as a case study. δD values of fluid inclusions in the calcite, and parent fluid δ18O values reconstructed from clumped isotope palaeothermometry, gave values which could represent a range of fluid sources: metamorphic or magmatic fluids, or surface waters which had undergone much fluid-rock interaction. Trace elements showed no distinctive patterns and shed no further light on fluid source. LA-ICP-MS U-Pb dating determined the vein calcite precipitation age – 318±30 Ma – which rule out metamorphic or magmatic fluid sources as no metamorphic or magmatic activity was occurring in the area at this time. The vein fluid source was therefore a surface water (meteoric based on paleogeographic reconstruction) which had undergone significant water-rock interaction. This study highlights the importance of combining the recently developed LA-ICP-MS U-Pb calcite geochronometer with stable isotopes and trace elements to help determine fluid sources of veins, and indeed any geological feature where calcite precipitated from a fluid that may have resided in the crust for a period of time (e.g. fault precipitates or cements)

Increased stocking rate and associated strategic dry-off decision rules reduced the amount of nitrate-N leached under grazing

peer-reviewedThe effect of intensive agricultural systems on the environment is of increasing global concern, and recent review articles have highlighted the need for sustainable intensification of food production. In grazing dairy systems, the leaching of nitrate-N (NO3-N) to groundwater is a primary environmental concern. A herd-level factor considered by many to be a key contributor to the amount of NO3-N leached from dairy pastures is stocking rate (SR), and some countries have imposed limits to reduce the risk of NO3-N loss to groundwater. The objective of the current experiment was to determine the effect of dairy cow SR on NO3-N leached in a grazing system that did not import feed from off-farm and had the same N fertilizer input. Five SR were evaluated (2.2, 2.7, 3.1, 3.7, and 4.3 cows/ha) in a completely randomized design (i.e., 2 replicates of each SR as independent farmlets) over 2 y. Pasture utilization, milk production/hectare, and days in milk/hectare increased with SR, but days in milk/cow and milk production/cow declined. The concentration of NO3-N in drainage water and the quantity of NO3-N leached/ha per year declined linearly with increasing SR, and the operating profit/kg NO3-N leached per ha increased. Higher SR was associated with fewer days in milk/cow, resulting in a reduction in estimated urine N excretion/cow (the main source of N leaching) during the climatically sensitive period for NO3-N leaching (i.e., late summer to winter). We hypothesized that the reduction in estimated urine N excretion per cow led to an increase in urinary N spread and reduced losses from urine patches. The results presented indicate that lowering SR may not reduce nitrate leaching and highlight the need for a full farm system-level analysis of any management change to determine its effect on productivity and environmental outcomes

Assessing sulfate reduction and methane cycling in a high salinity pore water system in the northern Gulf of Mexico

This paper is not subject to U.S. copyright. The definitive version was published in Marine and Petroleum Geology 25 (2008): 942-951, doi:10.1016/j.marpetgeo.2008.01.016.Pore waters extracted from 18 piston cores obtained on and near a salt-cored bathymetric high in Keathley Canyon lease block 151 in the northern Gulf of Mexico contain elevated concentrations of chloride (up to 838 mM) and have pore water chemical concentration profiles that exhibit extensive departures (concavity) from steady-state (linear) diffusive equilibrium with depth. Minimum δ13C dissolved inorganic carbon (DIC) values of −55.9‰ to −64.8‰ at the sulfate–methane transition (SMT) strongly suggest active anaerobic oxidation of methane (AOM) throughout the study region. However, the nonlinear pore water chemistry-depth profiles make it impossible to determine the vertical extent of active AOM or the potential role of alternate sulfate reduction pathways. Here we utilize the conservative (non-reactive) nature of dissolved chloride to differentiate the effects of biogeochemical activity (e.g., AOM and/or organoclastic sulfate reduction) relative to physical mixing in high salinity Keathley Canyon sediments. In most cases, the DIC and sulfate concentrations in pore waters are consistent with a conservative mixing model that uses chloride concentrations at the seafloor and the SMT as endmembers. Conservative mixing of pore water constituents implies that an undetermined physical process is primarily responsible for the nonlinearity of the pore water-depth profiles. In limited cases where the sulfate and DIC concentrations deviated from conservative mixing between the seafloor and SMT, the δ13C-DIC mixing diagrams suggest that the excess DIC is produced from a 13C-depleted source that could only be accounted for by microbial methane, the dominant form of methane identified during this study. We conclude that AOM is the most prevalent sink for sulfate and that it occurs primarily at the SMT at this Keathley Canyon site.This work was supported by DOE’s National Energy Technology Laboratory, the Office of Naval Research, and the Naval Research Laboratory. J.W.P was supported by a USGS Mendenhall Postdoctoral Research Fellowship Program during preparation of this manuscript

Hydrography and circulation near the crest of the East Pacific Rise between 9° and 10°N

Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part I: Oceanographic Research Papers 58 (2011): 365-376, doi:10.1016/j.dsr.2011.01.009.Topography has a strong effect on the physical oceanography over the flanks and crests of the global mid-ocean ridge system. Here, we present an analysis of the hydrography and circulation near the crest of the East Pacific Rise (EPR) between 9◦ and 10◦N, which coincides with an integrated study site (ISS) of the RIDGE2000 program. The analysis is based primarily on survey and mooring data collected during the LADDER project, which aimed to investigate oceanographic and topographic influences on larval retention and dispersal in hydrothermal vent communities. Results indicate that the yearly averaged regional mean circulation is characterized by a westward drift of 0.5–1 cm·s−1 across the EPR axis and by north- and southward flows along the western and eastern upper ridge flanks, respectively. The westward drift is part of a basin-scale zonal flow that extends across most of the Pacific ocean near 10◦N, whereas the meridional currents near the ridge crest are a topographic effect. In spite of considerable mesoscale variability, which dominates the regional circulation and dispersal on weekly to monthly time scales, quasi-synoptic surveys carried out during the mooring deployment and recovery cruises indicate subinertial circulations that are qualitatively similar to the yearly averaged flow but associated with significantly stronger velocities. Weekly averaged mooring data indicate that the anticyclonically sheared along-flank flows are associated with core speeds as high as 10 cm·s−1 and extend ≈10 km off axis and 200m above the ridge-crest topography. Near the northern limit of the study region, the Lamont Seamount Chain rises from the western ridge flank and restricts along-EPR flow to five narrow passages, where peak velocities in excess of 20 cm·s−1 were observed. Outside the region of the ridge-crest boundary currents the density field over the EPR near 10◦N is characterized by isopycnals dipping into the ridge flanks. Directly above the EPR axis the ridge-crest boundary currents give rise to an isopycnal dome. During times of strong westward cross-EPR flow isopycnal uplift over the eastern flank causes the cross-ridge density field below the doming isopycnals to be asymmetric, with higher densities over the eastern than over the western flank. The data collected during the LADDER project indicate that dispersal of hydrothermal products from the EPR ISS on long time scales is predominantly to the west, whereas mesoscale variability dominates dispersal on weekly to monthly time scales, which are particularly important in the context of larval dispersal.Co-funding of the LADDER project by the biological and physical oceanography divisions of the National Science Foundation under grants OCE-0425361 and OCE-0424953 is gratefully acknowledged, as is support of J.W. Lavelle by NOAA’s Pacific Marine Environmental Laboratory and by the NOAA Vents Program

Clumped-isotope palaeothermometry and LA-ICP-MS U–Pb dating of lava-pile hydrothermal calcite veins

Calcite veins are a common product of hydrothermal fluid circulation. Clumped-isotope palaeothermometry is a promising technique for fingerprinting the temperature of hydrothermal fluids, but clumped-isotope systematics can be reset at temperatures of > ca. 100 °C. To model whether the reconstructed temperatures represent calcite precipitation or closed-system resetting, the precipitation age must be known. LA-ICP-MS U–Pb dating of calcite is a recently developed approach to direct dating of calcite and can provide precipitation ages for modelling clumped-isotope systematics in calcite veins. In this study, clumped-isotope and LA-ICP-MS U–Pb calcite analyses were combined in basalt-hosted calcite veins from three settings in Scotland. Samples from all three localities yielded precipitation temperatures of ca. 75–115 °C from clumped-isotope analysis, but veins from only two of the sites were dateable, yielding precipitation ages of 224 ± 8 Ma and 291 ± 33 Ma (2σ). Modelling from the dated samples enabled confident interpretation that no closed-system resetting had occurred in these samples. However, the lack of a precipitation age from the third location meant that a range of possible thermal histories had to be modelled meaning that confidence that resetting had not occurred was lower. This highlights the importance of coupling clumped-isotope thermometry and LA-ICP-MS U–Pb calcite dating in determining the temperature of hydrothermal fluids recorded in calcite veins. This paired approach is shown to be robust in constraining the timing and precipitation temperature of calcite formation, and thus for tracking hydrothermal processes

Twenty five years after KLS: A celebration of non-equilibrium statistical mechanics

When Lenz proposed a simple model for phase transitions in magnetism, he couldn't have imagined that the "Ising model" was to become a jewel in field of equilibrium statistical mechanics. Its role spans the spectrum, from a good pedagogical example to a universality class in critical phenomena. A quarter century ago, Katz, Lebowitz and Spohn found a similar treasure. By introducing a seemingly trivial modification to the Ising lattice gas, they took it into the vast realms of non-equilibrium statistical mechanics. An abundant variety of unexpected behavior emerged and caught many of us by surprise. We present a brief review of some of the new insights garnered and some of the outstanding puzzles, as well as speculate on the model's role in the future of non-equilibrium statistical physics.Comment: 3 figures. Proceedings of 100th Statistical Mechanics Meeting, Rutgers, NJ (December, 2008

Hopf algebras and Markov chains: Two examples and a theory

The operation of squaring (coproduct followed by product) in a combinatorial Hopf algebra is shown to induce a Markov chain in natural bases. Chains constructed in this way include widely studied methods of card shuffling, a natural "rock-breaking" process, and Markov chains on simplicial complexes. Many of these chains can be explictly diagonalized using the primitive elements of the algebra and the combinatorics of the free Lie algebra. For card shuffling, this gives an explicit description of the eigenvectors. For rock-breaking, an explicit description of the quasi-stationary distribution and sharp rates to absorption follow.Comment: 51 pages, 17 figures. (Typographical errors corrected. Further fixes will only appear on the version on Amy Pang's website, the arXiv version will not be updated.

GUP1 and its close homologue GUP2, encoding multi-membrane-spanning proteins involved in active glycerol uptake in Saccharomyces cerevisiae

Many yeast species can utilise glycerol, both as sole carbon source and as an osmolyte. In Saccharomyces cerevisiae, physiological studies have previously shown the presence of an active uptake system driven by electrogenic proton symport. We have used transposon mutagenesis to isolate mutants affected in the transport of glycerol into the cell. Here we present the identification of YGL084c, encoding a multi-membrane-spanning protein, as being essential for proton symport of glycerol into Saccharomyces cerevisiae. The gene is named GUP1 (Glycerol UPtake) and is important for growth on glycerol as carbon and energy source, as well as for osmotic protection by added glycerol, of a strain deficient in glycerol production. Another ORF, YPL189w, presenting a high degree of homology to YGL084c, similarly appears to be involved in active glycerol uptake in salt-containing glucose-based media in strains deficient in glycerol production. Analogously, this gene is named GUP2. To our knowledge, this is the first report on a gene product involved in active transport of glycerol in yeasts. Mutations with the same phenotypes occurred in two other open reading frames of previously unknown function, YDL074c and YPL180w.Comunidade Europeia (CE) - contract BIO4-CT95-0161