Determination of the Rare-Earth Elements and Yttrium In 37 International Silicate Reference Materials By Inductively Coupled Plasma-Atomic Emission Spectrometry

The rare-earth elements (REE) and yttrium have been determined in 37 international rock and mineral reference materials. Samples were prepared using conventional rock-dissolution techniques, and the REE and yttrium were separated from the other constituents using cation-exchange chromatography. The REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) and yttrium were determined simultaneously by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Results for four well-characterised USGS standard rocks agree favourably with "recommended" values and with REE determinations made previously by workers using ICP-AES, isotope dilution mass spectrometry, instrumental neutron activaton analysis and X-ray fluorescence spectrometry.
Les éléments de terres rares (TR) et yttrium ont été dosés dans 37 échantillons internationaux de réféence. Les échantillons ont été décomposés par dissolution acide et les TR séparés par résine échangeuse de cations. Les TR (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) et yttrium ont été dosés simultanément par la spectrométrie d'émission-plasma inductif. Les résultats obtenus pour quatre échantillons de référence bien charactérisés de I'USGS se comparent favorablement avec ceux obtenus par la spectrométrie d'émission-plasma, la dilution isotopique, I'activation neutronique et par la spectrométrie d'é fluorescence-X.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

Groundwater Resources In Hard Rock; Experiences from The Hvaler Study,Southeastern Norway

Investigations in a newly constructed subsea road tunnel in the Iddefjord granite at Hvaler and test-pumping of boreholes on land indicate that a topographic or geophysical anomaly is no guarantee of a substantially transmissive fracture zone. Many prominent fracture zones appear to have depressed transmissivity due to secondary swelling-clay mineral infillings. No current geophysical technique can adequately distinguish these zones from transmissive ones. Given that siting of boreholes on the basis of geology alone can be unreliable, hydrogeologists should concentrate on quantifying the chances of a successful boring, and optimizing those chances by sensible location, favourable borehole orientation and use of artificial enhancement techniques.     

A methodology for locating the original quarries used for constructing historical buildings: application to Málaga Cathedral, Spain

It is often necessary to locate the original quarry which supplied the stone for a particular historical building. This stones could be used for future restoration work and for testing in the laboratory (artificial aging tests, physical properties determination, control of the efficacy of conservation treatments, etc.). Generally, reviewing historical documentation gives information about the geographical setting of quarries and location of the stones in the monument, but this information needs to be proved by field and laboratory studies. The comparative study of stone from quarries and monuments should basically include the following: (1) mineralogical and petrographical studies; (2) the chemical analysis of major, minor and trace elements; (3)stable isotopes determinations; (4) physical properties of quarry materials and unweathered building stone (water absorption, ultrasound transmission velocity, porosity and porous system, density, bulk density, compressive strength, etc.). This methodology was applied to Málaga Cathedral stones represented in the main façade, towers, and the western zone of the terrace, which, according to historical literature, came from Almayate (Miocene–Pliocene limestones) and Cerro Coronado (Permotriassic sandstone) in Málaga. The conclusion of the comparative study carried out on quarries and building stones was consistent with the information available from the historical documentation.     

Genesis and evolution of the lithospheric mantle beneath the Buffalo Head Terrane, Alberta (Canada)

Mantle xenoliths and xenocrysts were retrieved from three of the 88–86 Ma Buffalo Hills kimberlites (K6, K11, K14) for a reconnaissance study of the subcontinental lithospheric mantle (SCLM) beneath the Buffalo Head Terrane (Alberta, Canada). The xenoliths include spinel lherzolites, one garnet spinel lherzolite, garnet harzburgites, one sheared garnet lherzolite and pyroxenites. Pyroxenitic and wehrlitic garnet xenocrysts are derived primarily from the shallow mantle and lherzolitic garnet xenocrysts from the deep mantle. Harzburgite with Ca-saturated garnets is concentrated in a layer between 135–165 km depth. Garnet xenocrysts define a model conductive paleogeotherm corresponding to a heat flow of 38–39 mW/m². The sheared garnet lherzolite lies on an inflection of this geotherm and may constrain the depth of the lithosphere–asthenosphere boundary (LAB) beneath this region to ca 180 km depth.

A loss of >20% partial melt is recorded by spinel lherzolites and up to 60% by the garnet harzburgites, which may be related to lithosphere formation. The mantle was subsequently modified during at least two metasomatic events. An older metasomatic event is evident in incompatible-element enrichments in homogeneous equilibrated garnet and clinopyroxene. Silicate melt metasomatism predominated in the deep lithosphere and led to enrichments in the HFSE with minor enrichments in LREE. Metasomatism by small-volume volatile-rich melts, such as carbonatite, appears to have been more important in the shallow lithosphere and led to enrichments in LREE with minor enrichments in HFSE. An intermediate metasomatic style, possibly a signature of volatile-rich silicate melts, is also recognised. These metasomatic styles may be related through modification of a single melt during progressive interaction with the mantle. This metasomatism is suggested to have occurred during Paleoproterozoic rifting of the Buffalo Head Terrane from the neighbouring Rae Province and may be responsible for the evolution of some samples toward unradiogenic Nd and Hf isotopic compositions.

Disturbed Re–Os isotope systematics, evident in implausible model ages, were obtained in situ for sulfides in several spinel lherzolites and suggest that many sulfides are secondary (metasomatic) or mixtures of primary and secondary sulfides. Sulfide in one peridotite has unradiogenic ¹⁸⁷Os/¹⁸⁸Os and gives a model age of 1.89±0.38 Ga. This age coincides with the inferred emplacement of mafic sheets in the crust and suggests that the melts parental to the intrusions interacted with the lithospheric mantle.

A younger metasomatic event is indicated by the occurrence of sulfide-rich melt patches, unequilibrated mineral compositions and overgrowths on spinel that are Ti-, Cr- and Fe-rich but Zn-poor. Subsequent cooling is recorded by fine exsolution lamellae in the pyroxenes and by arrested mineral reactions.

If the lithosphere beneath the Buffalo Head Terrane was formed in the Archaean, any unambiguous signatures of this ancient origin may have been obliterated during these multiple events.     

Nanoscale study of As biomineralization in an acid mine drainage system

Spatial and seasonal variations of the oxidation of Fe(II) and As(III) have been previously documented in the Carnoulès (Gard, France) Acid Mine Drainage (AMD) by bulk analyses. These variations may be correlated with the variations in the activity of indigenous As(III)- and Fe(II)-oxidizing bacteria living in the As-rich Carnoulès water. The activity of these bacteria indeed plays an important role in the nature and composition of the solid phases that sequester arsenic at this site. In order to better understand the interactions of microbes with Fe and As in the Carnoulès AMD, we combined Transmission Electron Microscopy (TEM) and Scanning Transmission X-ray Microscopy (STXM) to collect near-edge X-ray absorption fine structure (NEXAFS) spectra at high spatial and energy resolution and to perform high spatial resolution imaging at the 30-50 nm scale. Spectromicroscopy was performed at the C K-edge, Fe L_2,3-edge, and As L_2,3-edge, which allowed us to locate living and/or mineralized bacterial cells and to characterize Fe and As oxidation states in the vicinity of those cells. TEM was used to image the same areas, providing higher resolution images and complementary crystallographic and compositional information through electron diffraction and EDXS analysis. This approach provides unique information on heterogeneous geochemical processes that occur in a complex microbial community in an AMD environment at the micrometer and submicrometer-scale. Bacterial cells in the Carnoulès AMD were frequently associated with mineral precipitates, and a variety of biomineralization patterns were observed. While many mineral precipitates were not associated with bacterial cells, they were associated with pervasive organic carbon. Finally, abundant biomineralized organic vesicles were observed in the Carnoulès AMD. Such vesicles may have been overlooked in highly mineralized extreme environments in the past and may represent an important component in a common biomineralization process in such environments.     

加拿大主要农田作物临界气象指标

根据加拿大主要农田作物生长发育对天气与气候条件的要求、农业气象学与气候学原理以及全球气候变化对农作物生产的影响和发展趋势,选择6个关键性气象因素(极端气温、强降水、强风、冷冻、土壤极端水分和作物生产有效热能条件),开发和评价12个农业气象临界指标(寒潮及热浪天数、日及旬最大降水量、日最大风速、强风天数、无霜期及冰冻期天数、标准降水系数、季节性水分亏缺、作物生长有效积温和累积热能单位).这些指标可供在该国各农产区科学规划和合理发展各类农田作物生产,包括喜暖性和喜凉性一年生草本作物,越冬性二年生及多年生草本及木本作物.该研究还依据该国这三类主要农田作物对临界温度和水分的需求,以及加拿大农田作物生长期和越冬期的天气和气候特征,建立了在任意农业生产年份中各类农田作物生长起始和终止日期的模式.本研究结果能用于指导该国将来在不同农产区适地适时种植适宜的农田作物和高效地经营与管理农场,同时可为农业生产咨询、政策制定和合理决策提供科学依据,也可供其他国家或地区开展类似的科学研究参考.     

The Seasonal Prediction of the Exceptional Yangtze River Rainfall in Summer 2020

During June and July of 2020, the Yangtze River basin suffered from extreme mei-yu rainfall and catastrophic flooding. This study explores the seasonal predictability and associated dynamical causes for this extreme Yangtze River rainfall event, based on forecasts from the Met Office GloSea5 operational forecast system. The forecasts successfully predicted above-average rainfall over the Yangtze River basin, which arose from the successful reproduction of the anomalous western North Pacific subtropical high (WNPSH). Our results indicate that both the Indian Ocean warm sea surface temperature (SST) and local WNP SST gradient were responsible for the westward extension of the WNPSH, and the forecasts captured these tropical signals well. We explore extratropical drivers but find a large model spread among the forecast members regarding the meridional displacements of the East Asian mid-latitude westerly jet (EAJ). The forecast members with an evident southward displacement of the EAJ favored more extreme Yangtze River rainfall. However, the forecast Yangtze River rainfall anomaly was weaker compared to that was observed and no member showed such strong rainfall. In observations, the EAJ displayed an evident acceleration in summer 2020, which could lead to a significant wind convergence in the lower troposphere around the Yangtze River basin, and favor more mei-yu rainfall. The model forecast failed to satisfactorily reproduce these processes. This difference implies that the observed enhancement of the EAJ intensity gave a large boost to the Yangtze River rainfall, hindering a better forecast of the intensity of the event and disaster mitigation.