Vapour transport of rare earth elements (REE) in volcanic gas: Evidence from encrustations at Oldoinyo Lengai

Fumarolic encrustations and natrocarbonatite lava from the active crater of Oldoinyo Lengai volcano, Tanzania, were sampled and analysed. Two types of encrustation were distinguished on the basis of their REE content, enriched (~ 2800–5600 × [REE_chondrite]) and depleted (~ 100–200 × [REE_chondrite]) relative to natrocarbonatite (1700–1900 × [REE_chondrite]. REE-enriched encrustations line the walls of actively degassing fumaroles, whereas REE-depleted encrustations occur mainly along cracks in and as crusts on cooling natrocarbonatite lava flows; one of the low REE encrustation samples was a stalactite from the wall of a possible fumarole. The encrustations are interpreted to have different origins, the former precipitating from volcanic gas and the latter from meteoric/ground water converted to steam by the heat of the overlying lava flow(s). REE-profiles of encrustations and natrocarbonatite are parallel, suggesting that there was no preferential mobilization of specific REE by either volcanic vapour or meteoric water vapour. The elevated REE-content of the first group of encrustations suggests that direct REE-transport from natrocarbonatite to volcanic vapour is possible. The REE trends observed in samples precipitating directly from the volcanic vapour cannot be explained by dry volatility based on the available data as there is no evidence in the encrustation compositions of the greatly enhanced volatility predicted for Yb and Eu. The observed extreme REE-fractionation with steep La/Sm slopes parallel to those of the natrocarbonatite reflects solvation and complexation reactions in the vapour phase that did not discriminate amongst the different REE or similar transport of REE in both the natrocarbonatite magma and its exsolving vapour. The low concentrations of REE in the encrustations produced by meteoric vapour suggest that the temperature was too low or that this vapour did not contain the ligands necessary to permit significant mobilization of the REE.     

Palaeoenvironment reconstruction,volcanic evolution and geochronology of the Cerro Blanco subcomplex,Nevados de Chillán volcanic complex,central Chile

Nevados de Chillán Volcanic Complex, central Chile, has been active for at least 640 ka—a period spanning a number of glacial and interglacial periods. Geologic mapping, radiometric dating and geochemical analysis have identified six new volcanic units and produced four new ⁴⁰Ar/³⁹Ar ages for Cerro Blanco, the northern subcomplex of Nevados de Chillán volcano. Compositions range from dacite to basaltic-andesite and a new geologic map is presented. Examination of lava fracture structures on both newly mapped lavas and those mapped during previous studies has enabled interpretations of former eruptive environments. Palaeoenvironment reconstructions, combined with ⁴⁰Ar/³⁹Ar ages and comparison with the marine oxygen isotope record, show that at least three phases of volcanic activity have occurred during the evolution of Cerro Blanco: (1) a constructive, pre-caldera collapse period; (2) a period of caldera formation and collapse; and (3) a constructive period of dome growth forming the modern day volcanic centre. This style of volcanic evolution, whereby large-scale caldera collapse is followed by growth of a new stratocone is common at Andean volcanoes.     

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.     

Benthic nutrient fluxes along the Laurentian Channel: Impacts on the N budget of the St. Lawrence marine system

Water column concentrations and benthic fluxes of dissolved inorganic nitrogen (DIN) and oxygen (DO) were measured in the Gulf of St. Lawrence and the Upper and Lower St. Lawrence Estuary (USLE and LSLE, respectively) to assess the nitrogen (N) budget in the St. Lawrence (SL) system, as well as to elucidate the impact of bottom water hypoxia on fixed-N removal in the LSLE. A severe nitrate deficit, with respect to ambient phosphate concentrations (N*∼−10 μmol L⁻¹), was observed within and in the vicinity of the hypoxic bottom water of the LSLE. Given that DO concentrations in the water column have remained above 50 μmol L⁻¹, nitrate reduction in suboxic sediments, rather than in the water column, is most likely responsible for the removal of fixed N from the SL system. Net nitrate fluxes into the sediments, derived from pore water nitrate concentration gradients, ranged from 190 μmol m⁻² d⁻¹ in the hypoxic western LSLE to 100 μmol m⁻² d⁻¹ in the Gulf. The average total benthic nitrate reduction rate for the Laurentian Channel (LC) is on the order of 690 μmol m⁻² d⁻¹, with coupled nitrification-nitrate reduction accounting for more than 70%. Using average nitrate reduction rates derived from the observed water column nitrate deficit, the annual fixed-N elimination within the three main channels of the Gulf of St. Lawrence and LSLE was estimated at 411 × 10⁶ t N, yielding an almost balanced N budget for the SL marine system.     

Beam forming on bottom-interacting tow-ship noise

Ship noise received on a horizontal array towed behind the ship is shown to be useful as a potentially diagnostic tool for estimating local acoustic bottom properties. In numerical simulations, tow-ship noise which bounces off the bottom is processed on a beamformer that shows the arrival angles; the beamformer output is readily interpreted by relating it to the Green's function of the acoustic wave equation. Simple signal processing is shown to be sufficient to extract the propagation angles of the "trapped" (i.e., propagating) modes of the acoustic waveguide. By relating the trapped modes to a basic geophysical model of the bottom, one can predict acoustic-propagation conditions for a particular bottom-interacting ocean acoustic environment.     

Time relationships between volcanism–plutonism–alteration–mineralization in Cu-stratabound ore deposits from the Michilla mining district,northern Chile: a <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronological approach

The Michilla mining district comprises one of the most important stratabound and breccia-style copper deposits of the Coastal Cordillera of northern Chile, hosted by the Middle Jurassic volcanic rocks of the La Negra Formation. ⁴⁰Ar/³⁹Ar analyses carried out on igneous and alteration minerals from volcanic and plutonic rocks in the district allow a chronological sequence of several magmatic and alteration events of the district to be established. The first event was the extrusion of a thick lava series of the La Negra Formation, dated at 159.9 ± 1.0 Ma (2σ) from the upper part of the series. A contemporaneous intrusion is dated at 159.6 ± 1.1 Ma, and later intrusive events are dated at 145.5 ± 2.8 and 137.4 ± 1.1 Ma, respectively. Analyzed alteration minerals such as adularia, sericite, and actinolite apparently give valid ⁴⁰Ar/³⁹Ar plateau and miniplateau ages. They indicate the occurrence of several alteration events at ca. 160–163, 154–157, 143–148, and 135–137 Ma. The first alteration event, being partly contemporaneous with volcanic and plutonic rocks, was probably produced in a high thermal gradient environment. The later events may be related either to a regional low-grade hydrothermal alteration/metamorphism process or to plutonic intrusions. The Cu mineralization of the Michilla district is robustly bracketed between 163.6 ± 1.9 and 137.4 ± 1.1 Ma, corresponding to dating of actinolite coexisting with early-stage chalcocite and a postmineralization barren dyke, respectively. More precisely, the association of small intrusives (a dated stock from the Michilla district) with Cu mineralization in the region strongly suggests that the main Michilla ore deposit is related to a magmatic/hydrothermal event that occurred between 157.4 ± 3.6 and 163.5 ± 1.9 Ma, contemporaneous or shortly after the extrusion of the volcanic sequence. This age is in agreement with the Re–Os age of 159 ± 16 Ma obtained from the mineralization itself (Tristá-Aguilera et al., Miner Depos, 41:99–105,2006).     

An assessment of the utility of staurolite in U-Pb dating of metamorphism

Pb isotope data, major and trace element compositions, fission track and synchrotron X-ray fluorescence analyses are presented for staurolites from nine pelitic schists in the continental United States to evaluate their potential use in U-Pb geochronology. Seven U-Pb analyses from Lanzirotti and Hanson (1995) are reexamined with respect to this additional data which was not available at the time. These data are then compared to 21 new U-Pb analyses of staurolite of varying composition from a variety of localities. The primary goals of this study are to: (1) evaluate the variability in U and Pb abundance and U/Pb ratio in staurolites of varying composition; (2) constrain how much of the measured U and Pb is derived from radiogenic solid inclusions such as monazite and zircon; (3) constrain how much of the measured U and Pb is derived from staurolite itself and evaluate any possible correlation of U and Pb abundance and U/Pb ratio to major element composition; (4) place preliminary constraints on closure temperature to Pb diffusion in staurolite; (5) evaluate how meaningful U-Pb ages can better be calculated for the low U/Pb ratio minerals. In the staurolite fractions analyzed U abundances range from 0.2 to 24.9 ppm, Pb from 0.13 to 2.41 ppm, the ²³⁸U/²⁰⁴Pb ratios vary from 135 to 9447, and the ²⁰⁶Pb/²⁰⁴Pb ratios from 23 to 623. For many of the fractions analyzed precise U-Pb ages can be calculated (±10 Ma or better) that appear to be consistent with available age constraints on the time of peak metamorphism. Mass balance calculations, fission track analysis, and synchrotron X-ray fluorescence trace element mapping show that although radiogenic inclusions are almost always present in large staurolite porphyroblasts, it is difficult for inclusions to account for the measured Pb isotopic compositions. It is also demonstrated that the U-Pb ages calculated for staurolites from Connecticut are at least 20 Ma older than nearby Rb-Sr muscovite and ⁴⁰Ar-³⁹Ar hornblende ages. This is consistent with staurolite having a closure temperature to U and Pb diffusion significantly higher than 500 °C. Received: 14 July 1995 / Accepted: 16 May 1997