He–Ar and Nd–Sr isotopic compositions of late Pleistocene felsic plutonic back arc basin rocks from Ulleungdo volcanic island, South Korea: Implications for the genesis of young plutonic rocks in a back arc basin

We report analyses of noble gases and Nd–Sr isotopes in mineral separates and whole rocks of late Pleistocene (< 0.2 Ma) monzonites from Ulleungdo, South Korea, a volcanic island within the back arc basin of the Japan island arc. A Rb–Sr mineral isochron age for the monzonites is 0.12 ± 0.01 Ma. K–Ar biotite ages from the same samples gave relatively concordant ages of 0.19 ± 0.01and 0.22 ± 0.01 Ma. ⁴⁰Ar/³⁹Ar yields a similar age of 0.29 ± 0.09 Ma. Geochemical characteristics of the felsic plutonic rocks, which are silica oversaturated alkali felsic rocks (av., 12.5 wt% in K₂O + Na₂O), are similar to those of 30 alkali volcanics from Ulleungdo in terms of concentrations of major, trace and REE elements. The initial Nd–Sr isotopic ratios of the monzonites (⁸⁷Sr/⁸⁶Sr = 0.70454–0.71264, ¹⁴³Nd/¹⁴⁴Nd = 0.512528–0.512577) are comparable with those of the alkali volcanics (⁸⁷Sr/⁸⁶Sr = 0.70466–0.70892, ¹⁴³Nd/¹⁴⁴Nd = 0.512521–0.512615) erupted in Stage 3 of Ulleungdo volcanism (0.24–0.47 Ma). The high initial ⁸⁷Sr/⁸⁶Sr values of the monzonites imply that seawater and crustally contaminated pre-existing trachytes may have been melted or assimilated during differentiation of the alkali basaltic magma.A mantle helium component (³He/⁴He ratio of up to 6.5 RA) associated with excess argon was found in the monzonites. Feldspar and biotite have preferentially lost helium during slow cooling at depth and/or during their transportation to the surface in a hot host magma. The source magma noble gas isotopic features are well preserved in fluid inclusions in hornblende, and indicate that the magma may be directly derived from subcontinental lithospheric mantle metasomatized by an ancient subduction process, or may have formed as a mixture of MORB-like mantle and crustal components. The radiometric ages, geochemical and Nd–Sr isotopic signatures of the Ulleungdo monzonites as well as the presence of mantle-derived helium and argon, suggests that these felsic plutonic rocks evolved from alkali basaltic magma that formed by partial melting of subcontinental lithospheric mantle beneath the back arc basin located along the active continental margin of the southeastern part of the Eurasian plate.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Exurbia from the bottom-up: Confronting empirical challenges to characterizing a complex system

We describe empirical results from a multi-disciplinary project that support modeling complex processes of land-use and land-cover change in exurban parts of Southeastern Michigan. Based on two different conceptual models, one describing the evolution of urban form as a consequence of residential preferences and the other describing land-cover changes in an exurban township as a consequence of residential preferences, local policies, and a diversity of development types, we describe a variety of empirical data collected to support the mechanisms that we encoded in computational agent-based models. We used multiple methods, including social surveys, remote sensing, and statistical analysis of spatial data, to collect data that could be used to validate the structure of our models, calibrate their specific parameters, and evaluate their output. The data were used to investigate this system in the context of several themes from complexity science, including have (a) macro-level patterns; (b) autonomous decision making entities (i.e., agents); (c) heterogeneity among those entities; (d) social and spatial interactions that operate across multiple scales and (e) nonlinear feedback mechanisms. The results point to the importance of collecting data on agents and their interactions when producing agent-based models, the general validity of our conceptual models, and some changes that we needed to make to these models following data analysis. The calibrated models have been and are being used to evaluate landscape dynamics and the effects of various policy interventions on urban land-cover patterns.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Fate and effects of a heavy fuel oil spill on a Georgia salt marsh

Addition of a heavy oil to a Spartina salt marsh in the autumn resulted in high concentrations of polycyclic aromatic hydrocarbons in sediment and benthic animals. The highest concentrations of phenanthrene, chrysene and fluoranthene in the sediment were 112, 105 and 75 ng/g sediment, respectively. These concentrations rapidly decreased during the 20 week period following the spill. The times for these hydrocarbons to decrease to 50% of their highest values, i.e. half-life, were approximately 100, 70 and 30 days in sediment, mussels and oysters, respectively. Benthic macrofauna species showed three responses to oil addition which included no change, an increase, or a decrease in the population. No changes were noted in populations of fiddler crabs (Uca pugnax), oysters (Crassostrea virginica), and mussels (Modiolus demissus). Mud snails (Nassarius obsoleta) increased in density after the spill due to immigration of adult snails from untreated areas to scavenge on animals killed by the oil. Many of the adult periwinkles (Littorina irrorata) were killed by the oil. In the spring, juvenile periwinkles recolonised to oiled areas as a result of larvae settling.     

An alkaline unwinding assay for the detection of DNA damage in aquatic organisms

This paper reports a rapid and facile procedure for obtaining of DNA from small, whole aquatic organisms (fathead minnow, Pimephales promelas) as well as from the liver of another species (bluegill sunfish, Lepomis macrochirus) and the subsequent estimation of its double strandedness. DNA was isolated from various tissues by homogenization in a basic pH solution containing detergent followed by differential extraction using organic solvents. Additional purification was accomplished by molecular sieve chromatography. Under defined alkaline unwinding conditions, the amount of double-stranded and single-stranded DNA was determined using the bisbenzimidazole dye Hoechst 33258. The technique was used to detect the occurrence of strand breaks in DNA of fathead minnows chemically exposed to benzo[a]pyrene.     

Generation of random waves in time-dependent extended mild-slope equations using a source function method

We develop techniques of numerical wave generation in the time-dependent extended mild-slope equations of Suh et al. [1997. Time-dependent equations for wave propagation on rapidly varying topography. Coastal Engineering 32, 91–117] and Lee et al. [2003. Extended mild-slope equation for random waves. Coastal Engineering 48, 277–287] for random waves using a source function method. Numerical results for both regular and irregular waves in one and two horizontal dimensions show that the wave heights and the frequency spectra are properly reproduced. The waves that pass through the wave generation region do not cause any numerical disturbances, showing usefulness of the source function method in avoiding re-reflection problems at the offshore boundary.