Phase relations of biotite and stilpnomelane in the greenschist facies

Phase relations of biotite and stilpnomelane and associated silicate minerals have been studied in rocks of the greenschist facies, chiefly from Otago, New Zealand and western Vermont, but also from Scotland, Minnesota-Michigan iron range, and northwest Washington. That stilpnomelane in the greenschicht facies crystallizes initially with nearly all iron in the ferrous state is indicated by chemical analyses, high p-T experiments, and phase relationships. Alteration of stilpnomelane after metamorphism not only oxidizes iron but leaches potassium; corrections for both effects must be made in using analyses of brown stilpnomelane in studies of phase relations. Two discontinuous reactions which produce biotite at the biotite isograd have been identified:

1. muscovite+stilpnomelane+actinolite→ biotite+chlorite+epidote
2. chlorite+microcline→ biotite+muscovite. Biotite produced by the first of these reactions has a limited range of variation in Fe/Mg. As grade advances within the biotite zone more magnesian and ferruginous biotites become stable in consequence of the two continuous reactions:
3. muscovite+actinolite+chlorite→ biotite (Mg-rich)+epidote
4. muscovite+stilpnomelane→ biotite (Fe-rich)+chlorite.

Stilpnomelane is stable in muscovite-free rocks throughout the biotite zone, and even up to the grade at which hornblende becomes stable. Phengitic muscovite is stable throughout the biotite zone in New Zealand and thus apparently does not contribute to the formation of biotite until a higher grade is reached.     

Use of in situ-produced Be in carbonate-rich environments: A first attempt

We have determined the production rate of in situ-produced ¹⁰Be in calcite through measurements of ¹⁰Be and ³⁶Cl concentrations in the same calcite samples and of ¹⁰Be concentrations in depth profiles of flint from the same erosional surface. This yields a ¹⁰Be production rate in calcite of 37.9 ± 6.0 at/g/yr at sea level and high latitude, approximately sixfold higher than production in the coexisting flint. We propose that this higher rate of production may be due to high production cross sections for C spallation by cosmic rays with energies below 50 MeV. These results also open the possibility of dating burial events in carbonate-rich environments by differential radioactive decay of ¹⁰Be and ³⁶Cl.     

Detecting groundwater contamination of a river in Georgia, USA using baseflow sampling

Algal blooms and fish kills were reported on a river in coastal Georgia (USA) downstream of a poultry-processing plant, prompting officials to conclude the problems resulted from overland flow associated with over-application of wastewater at the plant’s land application system (LAS). An investigation was undertaken to test the hypothesis that contaminated groundwater was also playing a significant role. Weekly samples were collected over a 12-month period along an 18 km reach of the river and key tributaries. Results showed elevated nitrogen concentrations in tributaries draining the plant and a tenfold increase in nitrate in the river between the tributary inputs. Because ammonia concentrations were low in this reach, it was concluded that nitrate was entering via groundwater discharge. Data from detailed river sampling and direct groundwater samples from springs and boreholes were used to isolate the entry point of the contaminant plume. Analysis showed two separate plumes, one associated with the plant’s unlined wastewater lagoon and another with its LAS spray fields. The continuous discharge of contaminated groundwater during summer low-flow conditions was found to have a more profound impact on river-water quality than periodic inputs by overland flow and tributary runoff.     

Paleoclimatic implications of glacial and postglacial refugia for Pinus pumila in western Beringia

Palynological results from Julietta Lake currently provide the most direct evidence to support the existence of a glacial refugium for Pinus pumila in mountains of southwestern Beringia. Both percentages and accumulation rates indicate the evergreen shrub survived until at least ∼ 19,000 ¹⁴C yr BP in the Upper Kolyma region. Percentage data suggest numbers dwindled into the late glaciation, whereas pollen accumulation rates point towards a more rapid demise shortly after ∼ 19,000 ¹⁴C yr BP. Pinus pumila did not re-establish in any great numbers until ∼ 8100 ¹⁴C yr BP, despite the local presence ∼ 9800 ¹⁴C yr BP of Larixdahurica, which shares similar summer temperature requirements. The postglacial thermal maximum (in Beringia ∼ 11,000-9000 ¹⁴C yr BP) provided Pinus pumila shrubs with equally harsh albeit different conditions for survival than those present during the LGM. Regional records indicate that in this time of maximum warmth Pinus pumila likely sheltered in a second, lower-elevation refugium. Paleoclimatic models and modern ecology suggest that shifts in the nature of seasonal transitions and not only seasonal extremes have played important roles in the history of Pinus pumila over the last ∼ 21,000 ¹⁴C yr BP.     

Beryllium-10 in Australasian tektites: Constraints on the location of the source crater

By using accelerator mass spectrometry we have measured the ¹⁰Be concentrations of 86 Australasian tektites. Corrected to the time of tektite production ∼0.8 My ago, the ¹⁰Be concentrations (10⁶ atom/g) range from 59 for a layered tektite from Huai Sai, Thailand, to 280 for an australite from New South Wales, Australia. The average value is 143 ± 50. When tektites are sorted by country, their average measured ¹⁰Be concentrations increase slowly with increasing distance from Southeast Asia, the probable location of the tektite producing event, from 59 ± 9 for 6 layered tektites from Laos to 136 ± 20 for 20 splash-form tektites from Australia. The lowest ¹⁰Be concentrations for tektites fall on or within a contour centered off the shore of Vietnam, south of the Gulf of Tonkin (107°E; 17°N), but also encompassing two other locations in the area of northeastern Thailand previously proposed for the site of a single tektite-producing impact. The ¹⁰Be concentrations of layered tektites show only a weak anticorrelation (R ∼ −0.3) with the numbers of relict crystalline inclusions.Loosely consolidated, fine-grained terrestrial sediments or recently consolidated sedimentary rocks are the most likely precursor materials. Dilution of sediments with other kinds of rock raises problems in mixing and is not supported by petrographic data. Sedimentary columns that have the right range of ¹⁰Be concentrations occur off the coasts of places where sedimentation rates are high relative to those in the deep sea. A single impact into such a region, 15 to 300 m thick, could have propelled near-surface, high-¹⁰Be material farthest—to Australia—while keeping the deeper-lying, low-¹⁰Be layers closer to home. We do not rule out, however, other proposed mechanisms for tektite formation.     

Evidence for Neotethys rooted within the Vardar suture zone from the Voras Massif, northernmost Greece

Three conflicting models are currently proposed for the location and tectonic setting of the Eurasian continental margin and adjacent Tethys ocean in the Balkan region during Mesozoic–Early Tertiary time. Model 1 places the Eurasian margin within the Rhodope zone relatively close to the Moesian platform. A Tethyan oceanic basin was located to the south bordering a large “Serbo-Pelagonian” microcontinent. Model 2 correlates an integral “Serbo-Pelagonian” continental unit with the Eurasian margin and locates the Tethys further southwest. Model 3 envisages the Pelagonian zone and the Serbo-Macedonian zone as conjugate continental units separated by a Tethyan ocean that was sutured in Early Tertiary time to create the Vardar zone of northern Greece and former Yugoslavia. These published alternatives are tested in this paper based on a study of the tectono-stratigraphy of a completely exposed transect located in the Voras Mountains of northernmost Greece. The outcrop extends across the Vardar zone, from the Pelagonian zone in the west to the Serbo-Macedonian zone in the east.Within the Voras Massif, six east-dipping imbricate thrust sheets are recognised. Of these, Units 1–4 correlate with the regional Pelagonian zone in the west (and related Almopias sub-zone). By contrast, Units 5–6 show a contrasting tectono-stratigraphy and correlate with the Paikon Massif and the Serbo-Macedonian zone to the east. These units form a stack of thrust sheets, with Unit 1 at the base and Unit 6 at the top. Unstacking these thrust sheets places ophiolitic units between the Pelagonian zone and the Serbo-Macedonian zone, as in Model 3. Additional implications are, first, that the Paikon Massif cannot be seen as a window of Pelagonian basement, as in Model 1, and, secondly, Jurassic andesitic volcanics of the Paikon Massif locally preserve a gneissose continental basement, ruling out a recently suggested origin as an intra-oceanic arc.We envisage that the Almopias (Vardar) ocean rifted in Triassic time, followed by seafloor spreading. The Almopias ocean was consumed beneath the Serbo-Macedonian margin in Jurassic time, generating subduction-related arc volcanism in the Paikon Massif and related units. Ophiolites were emplaced onto the Pelagonian margin in the west and covered by Late Jurassic (pre-Kimmeridgian) conglomerates. Other ophiolitic rocks formed within the Vardar zone (Ano Garefi ophiolite, Unit 4) in latest Jurassic–Early Cretaceous time and were not deformed until Early Tertiary time. The Vardar zone finally sutured in the Early Tertiary creating the present imbricate thrust structure of the Voras Mountains.     

Biogenic nanoparticulate UO2: Synthesis, characterization, and factors affecting surface reactivity

The surface reactivity of biogenic, nanoparticulate UO₂ with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO₂. Synthesis of biogenic UO₂ was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO₂ as a function of particle size and surface-associated organic matter. The N₂-BET surface areas of the two biogenic UO₂ samples following the washing procedures are 128.63 m² g⁻¹ (NAUO2) and 92.56 m² g⁻¹ (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO₂ (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U L_III-edge EXAFS spectra for biogenic UO₂ (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO₂. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO₂ is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m⁻² UO₂ (bulk uraninite), 2.34 ± 0.12 μmol m⁻² UO₂ (NAUO2), and 2.57 ± 0.10 μmol m⁻² UO₂ (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO₂ indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)₆ sorbs as bidentate, edge-sharing complexes to UO₈ polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO₂ surface. Surface-associated organic matter on the biogenic UO₂ particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO₂ surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.     

A methodology for making initial estimates of groundwater recharge from groundwater vulnerability mapping

Recharge to an aquifer can be estimated by first calculating the effective rainfall using a soil moisture budgeting technique, and then by applying a recharge coefficient to indicate the proportion of this effective rainfall that contributes to groundwater recharge. In the Republic of Ireland, the recharge coefficient is determined mainly by the permeability and thickness of the superficial deposits (subsoils) that overlie the country’s aquifers. The properties of these subsoils also influence groundwater vulnerability, and a methodology has been developed for determining the recharge coefficient using the groundwater vulnerability classification. The results of four case studies have been used to develop a quantified link between subsoil permeability, aquifer vulnerability, recharge and runoff. Recharge and runoff coefficients are each classed into three groupings: high, intermediate and low. A high recharge coefficient equates to a low runoff coefficient, and vice versa. A GIS-based tool enables preliminary estimates of recharge to be made using these recharge coefficient groupings. Potential recharge is calculated as the product of effective rainfall and recharge coefficient. The actual recharge is then calculated taking account of the ability of the aquifer to accept the available recharge. The methodology could be applied to other temperate climate zones where the main aquifers have a substantial covering of superficial deposits.