Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

Experimente zum Einfluß des Gesteinsglas-Chemismus auf die Zeolithbildung durch hydrothermale Umwandlung

In the formation of zeolites by hydrothermal alteration volcanic glasses are the starting material in most cases. The experiments aimed at demonstrating in what way the chemistry of the volcanic glass influences:

1. the alteration rate of the volcanic glass to zeolites,
2. the kind of zeolites being formed and their formation conditions.

Three volcanic glasses were used, a basaltic, a phonolitic, and a rhyolitic one. The experimental conditions were as similar as possible to the natural alteration conditions. Solutions being used: H₂O dist (pH ～5.5), 0.01 n NaOH (pH ～10.5), and solutions of similar chemistry to the natural ones. The temperatures were 180 °, 200 °, 250 ° C. The experiments were carried out both in closed and in open systems. The experimental results show a difference in the alteration rate and in the zeolites being formed between the basaltic and the phonolitic glasses on the one hand and the rhyolitic one on the other. In case of the closed system the SiO₂-poor volcanic glasses react more rapidly than the SiO₂-rich one. The zeolites being formed are chabazite, phillipsite, analcime respectively mordenite, analcime. In case of the open system the influence of the chemistry of the volcanic glass on the alteration rate and the zeolite being formed is less significant. Which zeolite is formed at a given temperature depends on: the chemistry of the starting material, the chemistry of the reacting solution and wether there is a closed or an open system.     

湖光岩玛珥湖火山灰的成分及其来源

湖光岩玛珥湖沉积物中的火山灰保存了其原始形貌、原生的沉积和成分特征,是进行岩芯沉积物对比和定年的理想材料之一。除了对火山灰进行常规的定年外,通过精确测定火山灰中玻璃碎屑(玻屑)的成分,并与已知时代的火山喷发物成分对比确定火山灰的年龄已成为火山灰年代学研究的重要领域之一,因为它能够区分年龄差别在同位素定年误差之内的数层火山灰。本文利用电子探针分析了湖光岩玛珥湖岩芯火山灰中玻屑的成分,经与全球年龄已知火山喷发物的成分对比和分析,认为该火山灰的年龄为74000aB.P.,在此基础上,讨论了湖光岩玛珥湖岩芯74000aB.P.以来沉积速率的变化趋势。     

Sedimentary petrology and geochemistry of siliciclastic rocks from the upper Jurassic Tordillo Formation (Neuquén Basin, western Argentina): Implications for provenance and tectonic setting

The Upper Jurassic Tordillo Formation is exposed along the western edge of the Neuquén Basin (west central Argentina) and consists of fluvial strata deposited under arid/semiarid conditions. The pebble composition of conglomerates, mineralogical composition of sandstones and pelitic rocks, and major- and trace-element geochemistry of sandstones, mudstones, and primary pyroclastic deposits are evaluated to determine the provenance and tectonic setting of the sedimentary basin. Conglomerates and sandstones derived almost exclusively from volcanic sources. The stratigraphic sections to the south show a clast population of conglomerates dominated by silicic volcanic fragments and a predominance of feldspathic litharenites. This framework composition records erosion of Triassic–Jurassic synrift volcaniclastic rocks and basement rocks from the Huincul arch, which was exhumed as a result of Late Jurassic inversion. In the northwestern part of the study area, conglomerates show a large proportion of mafic and acidic volcanic rock fragments, and sandstones are characterised by a high content of mafic volcanic rock fragments and plagioclase. These data suggest that the source of the sandstones and conglomerates was primarily the Andean magmatic arc, located west of the Neuquén Basin. The clay mineral assemblage is interpreted as the result of a complex set of factors, including source rock, climate, transport, and diagenesis. Postdepositional processes produced significant variations in the original compositions, especially the fine-grained deposits. The Tordillo sediments are characterised by moderate SiO₂ contents, variable abundances of K₂O and Na₂O, and a relatively high proportion of ferromagnesian elements. The degree of chemical weathering in the source area, expressed as the chemical index of alteration, is low to moderate. The major element geochemistry and Th/Sc, K/Rb, Co/Th, La/Sc, and Cr/Th values point to a significant input of detrital volcanic material of calcalkaline felsic and intermediate composition. However, major element geochemistry is not useful for interpreting the tectonic setting. Discrimination plots based on immobile trace elements, such as Ti, Zr, La, Sc, and Th, show that most data lie in the active continental margin field. Geochemical information is not sufficiently sensitive to differentiate the two different source areas recognized by petrographic and modal analyses of conglomerates and sandstones.     

Compositional variation in magma through early neogene in the Northeast Indian Ocean: A testimony from glass shards

We report unusual occurrence of glass shards with diverse morphologies and compositions in the volcanic ash associated with the early Neogene marine stratigraphic succession (early Miocene to early middle Miocene) of Andaman-Nicobar Islands, Northeast Indian Ocean. These small, ash-size (200 to 800 μm) broken pieces of glass shards when viewed under Scanning Electron Microscope (SEM), represent distinctive — platy, sickle, bicuspate, concentric, angular, horn shape and slivers with broken angular bubble wall — morphologies. Glass shards are colourless. But, a few are grey or reddish-brown, indicate high Fe content. Chilled, juvenile, angular and blocky shards show fragments of highly viscous, silicic magma. Spindle and ribbon-shape shards form from a low viscosity basalt and rhyolite. Electron Probe Micro Analyzer (EPMA) was used to measure low concentration variations of major oxides within individual amorphous silicate solid glass shards whose disordered atomic structure is that of a liquid derived from a silicate melt. Major elemental chemistry of early Miocene glass shards from Colebrook island show low silica, alkalis, high FeO_(T) MgO and CaO, whereas, early middle Miocene glass shards from Inglis island show high silica, alkalis, low FeO_(T), MgO and CaO contents. These data-sets when plotted on ternary TotalAlkali-Silica and Na₂O+K₂O-MgO-FeO_(T) diagrams show that their data plots lie within the basaltic-andesite, tephri-phonolite, rhyolite and trachyte fields. These glass shards which were present in the provenance, formed by explosive eruption of lavas, ranging in composition from basalt to rhyolite with andesite/ basalt-andesite being the most common magma types erupted sub-areally, implying island arc type of tectono-magmatic setting for the formation of these lavas. However, more evolutionary variant rhyolite was most likely formed by crystal fractionation.     

The use of sorting curves in studying K2O alteration in interbedded greywacke and argillite

The chemical composition of unaltered greywacke-argillite sequences varies both abruptly and gradationally across short distances of a few centimeters to meters. These original variations are sufficient to mask changes in K₂O (and other oxides) resulting from hydrothermal alteration. Sorting curves for unaltered samples present K₂O contents in terms of two relatively immobile oxides SiO₂ and Al₂O₃. This allows an estimated of the original pre-alteration K₂O content of altered samples, from which gains and losses can then be calculated.     

松辽盆地营城组两类酸性火山岩地球化学特征与成因

松辽盆地断陷期营城组发育一套厚层火山岩,钻井岩心及薄片观察发现,火山岩以流纹岩、英安岩、流纹质凝灰岩及熔结凝灰岩等酸性火山岩为主,中基性岩相对较少。在对样品精细挑选基础上,开展了岩石主量元素、微量元素及Sr-Nd同位素测试分析。结果显示,该套酸性火山岩依据TiO2含量可明显分为两类,其中高Ti酸性火山岩(TiO2>0.45%),规模较小,SiO2含量介于64.87%～68.79%之间,其主量元素、微量元素与亚碱性中基性岩呈连续变化趋势且具有相似的Sr-Nd同位素组成;低Ti酸性火山岩(TiO2<0.4%)SiO2含量为68.93%～76.69%,该类岩石为营城组酸性火山岩主体,与碱性基性岩呈双峰式组合,元素含量及同位素比值变化范围较大。研究表明,两类酸性火山岩的形成都与晚中生代东北地区受古太平洋板块俯冲引起的岩石圈拆沉减薄软流圈上涌有关。在板块俯冲影响下,被富集的亏损地幔源区发生部分熔融,在岩浆演化过程中经历了一定分离结晶作用形成了少量高Ti酸性火山岩岩浆。与此同时,在底侵作用下新生地壳与下地壳物质发生混合熔融,受上地壳不同程度混染后形成了大规模的低Ti酸性火山岩岩浆。     

Alteration of volcanic matter in deep sea sediments: evidence from the chemical composition of interstitial waters from deep sea drilling cores

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H₂¹⁸O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H₂¹⁸O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.     

The North Fork porphyry copper deposit of the Washington Cascades

The North Fork porphyry copper deposit in the Cascade volcanic arc of Washington displays copper mineralization confined to the potassic (biotite) and phyllic (sericite) alteration zones. No secondary potassium feldspars have been found in either alteration zone; moreover, chemical analyses indicate the potassic alteration zone contains a low K₂O content. Argillic and propylitic zones are also recognized, but these are barren of hypogene copper mineralization. Biotite-chalcopyrite intergrowths in the deposit have been given a 9.9 K-Ar age. Thus it is not only one of the youngest deposits dated in the western Cordillera, but it is associated with a volcanic arc which has no current Benioff zone seismic array or accompanying trench. The deposit appears to have developed during the period when coupling of the North American and Juan de Fuca plates probably inhibited subduction under the Cascade volcanic arc.     

中昆仑造山带钾玄岩质火山岩的地质、地球化学和时代

 本文论述了中昆仑(北坡)4个地区第四纪火山岩的地质产状、岩石学、地球化学特征及时代。这一套岩石以安粗岩类为主,普遍含有普通辉石和斜长石斑晶,少数还有橄榄石、紫苏辉石或石英、透长石、黑云母斑晶。在化学上以富碱尤其富钾为突出特点,K₂O/Na₂O≥1,而且 Rb、Sr、Ba 等低场强元素和 LREE 也强烈富集,构成一个连续的钾玄岩系列(Shoshoaite Serics)。区域构造,地球化学和深源捕虏体的证据表明,本区钾玄质岩浆来自于上地幔的低度部分熔融,并受到地壳的同化和污染。火山活动大致从晚第三纪开始一直延续到第四纪,特别是中、晚更新世最为剧烈,是昆仑山及青藏高原快速隆升的新构造运动表现形式之一。     

Petrogenesis and timing of emplacement of porphyritic monzonite,dolerite, and basalt associated with the Kuoerzhenkuola Au deposit,Western Junggar,NW China: implications for early Carboniferous tectonic setting and Cu–Au mineralization prospectivity

ABSTRACT

The Kuoerzhenkuola epithermal Au deposit is located in the northern part of the West Junggar region of NW China and is underlain by a recently discovered porphyritic monzonite intrusion that contains Cu–Au mineralization. Zircon LA-ICP-MS U–Pb dating of this intrusion yielded an age of 350 ± 4.7 Ma. The porphyritic monzonite is calc-alkaline and is characterized by high concentrations of Sr (583–892 ppm), significant depletions in the heavy rare earth elements (HREE; e.g. Yb = 0.96–2.57 ppm) and Y (10.4–23.3 ppm), and primitive mantle-normalized multi-element variation diagram patterns with positive Sr and Ba and negative Nb and Ti anomalies, all of which indicate that this intrusion is compositionally similar to adakites elsewhere. The composition of the porphyritic monzonite is indicative of the derivation from magmas generated by the melting of young subducted slab material. The area also contains Nb-enriched basalts that are enriched in sodium (Na₂O/K₂O = 1.20–3.90) and have higher Nb, Zr, TiO₂, and P₂O₅ concentrations and Nb/La and Nb/U ratios than typical arc basalts. The juxtaposition of adakitic rocks, Nb-enriched basalts, and dolerites in this region suggests that the oceanic crust of the expansive oceans within the West Junggar underwent early Carboniferous subduction. Magnetite is widespread throughout the Kuoerzhenkuola Au deposit, as evidenced by the volcanic breccias cemented by late hydrothermal magnetite and pyrite. In addition, the zoned potassic, quartz-sericite alteration, and propylitic and kaolin alteration in the deeper parts of the porphyritic monzonite are similar to those found in porphyry Cu–Au deposits. These findings, coupled with the mineralogy and geochemistry of the alteration associated with the Kuoerzhenkuola Au deposit, suggest that the mineralization in this area is not purely epithermal, with the geology and geochemistry of the porphyritic monzonite in this area suggesting that a porphyry Cu–Au deposit is probably located beneath the Kuoerzhenkuola Au deposit.     

新疆天山地区榆树沟-铜花山蛇绿岩特征和构造背景

榆树沟-铜花山蛇绿岩出露于南天山北缘,属哈萨克斯坦-伊犁板块和塔里木板块之间的缝合带。蛇绿岩已被构造肢解,主要由超镁铁岩、堆晶岩、熔岩类组成。超镁铁岩以方辉橄榄岩为主,显示典型的亏损地幔岩特征,橄榄石为富镁型,Fo为90;斜方辉石为顽火辉石,En为90,单斜辉石含量少;副矿物铬尖晶石属低铬型,Cr^#值(＝Cr/(Cr+Al)×100)16~28,Mg^#值(=Mg/(Mg+Fe)×100)63~75,反映了深海橄榄岩特征。归一化后榆树沟超镁铁岩MgO含量38.84%~44.53%,Al₂O₃为1.51%~3.63%,CaO为0.42%~5.77%,成分近于大洋二辉橄榄岩;铜花山的超镁铁岩叠加碳酸岩化,LREE强烈富集,可能经历了俯冲洋壳流体改造。熔岩类在榆树沟和铜花山均有较大规模产出,其中榆树沟玄武岩为主,铜花山安山岩和英安岩较多。熔岩多已遭受绿片岩相海底热液蚀变。榆树沟玄武岩的REE含量总体比铜花山的低,稀土配分模式均为轻稀土富集型;玄武岩的微量元素特征表明其源区可能遭受过流体作用影响。铜花山三个高镁火山岩化学成份具有SiO₂(32%~36%)含量很低、MgO(20.12%~28.50%)含量高、K₂O+Na₂O(0.06%~0.46%)含量小于2%的特征,综合分析可归为苦橄岩类。堆晶岩通常以构造小岩块产在超镁铁岩块中或基性熔岩中,以辉长岩为主,有少量橄榄辉石岩等,岩石蚀变、构造变形强烈。堆晶岩的成分接近玄武岩,存在LREE富集和略亏损平坦两种类型。岩石地球化学特征表明榆树沟和铜花山的蛇绿岩形成于MOR构造环境,但具有受俯冲带流体改造特征,并伴生有岛弧火山岩。     

Lithogeochemical and mineralogical indicators of Andean precious-metal and polymetallic vein mineralization

Proximal and distal lithogeochemical alteration patterns associated with precious-metal and polymetallic vein mineralization in the Andes of Bolivia and Peru are delineated both by sulphophile elements such as Ag, As, Pb, S, Sb, Sn and Zn, and also by hydrothermal alteration indicators such as CaO/MgO, K₂O/Na₂O, Rb/K and Rb/Sr. In some cases, single-element, ratio and normalized data additive plots permit the detection of a vein at a distance of more than 100 m even when the visible alteration extends for less than 10 m. Asymmetric hanging-wall-footwall halos in both volcanic and sedimentary rocks provide a useful supra-ore/sub-ore indicator for inclined veins. The K₂O/Na₂O ratio appears to be the most reliable lithogeochemical guide to ore-related hydrothermal alteration.     

Effects of the degree of polymerization on the structure of sodium silicate and aluminosilicate glasses and melts: An O NMR study

Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report ¹⁷O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na₂O/SiO₂ ratio and Na₂O/Al₂O₃ ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na₂O-k(SiO₂)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na₂O/SiO₂ ratio (k), as predicted from the composition. The ¹⁷O isotropic chemical shifts (¹⁷O δ_iso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO₂ content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO₂ content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO₂ content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na₂O]_x[Al₂O₃]_1−xSiO₂, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al₂O₃ content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al₂O₃ content at a constant mole fraction of SiO₂. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO₂.     

Regional-scale hydrothermal alteration in the Central Blake River Group,western Abitibi subprovince,Canada: implications for VMS prospectivity

The Late Archean Blake River Group is a thick succession of predominantly mafic volcanic rocks within the southern zone of the Abitibi greenstone belt. It contains a number of silicic volcanic centers of different size, including the large Noranda volcanic complex, which is host to 17 past-producing volcanogenic massive sulfide deposits. The Noranda complex consists of a 7- to 9-km-thick succession of bimodal mafic and felsic volcanic rocks erupted during five major cycles of volcanism. Massive sulfide formation coincided with a period of intense magmatic activity (cycle III) and the formation of the Noranda cauldron. Hydrothermal alteration in these rocks is interpreted to reflect large-scale hydrothermal fluid flow associated with rapid crustal extension and rifting of the volcanic complex. The alteration includes abundant albite, chlorite, epidote and quartz (silicification), which exhibit broad stratigraphic and structural control and correlate with previously mapped whole-rock oxygen isotope zonation. The Mine Sequence volcanic rocks are characterized by abundant iron-rich chlorite (Fe/Fe+Mg >0.5), hydrothermal amphibole (ferroactinolite) and coarse-grained epidote of clinozoisite composition (<10 wt% Fe ₂O ₃). Volcanic rocks of the pre-cauldron sequences, which contain only subeconomic stringer mineralization, are characterized by less abundant chlorite and mainly fine-grained epidote (>10 wt% Fe ₂O ₃) lacking the clinozoisite solid solution. Alteration in the Mine Sequence volcanic rocks persists along strike well beyond the limits of the main ore deposits (as far as several tens of kilometers) and can be readily distinguished from greenschist facies metamorphic assemblages at a regional scale. The lack of similar alteration in the pre-cauldron sequences is consistent with limited ¹⁸O-depletion and suggests that the early history of the volcanic complex did not support large-scale, high-temperature fluid flow in these rocks. Comparisons with a much smaller, barren volcanic complex in nearby Ben Nevis township reveal important differences in the alteration mineralogy between volcanoes of different size, with implications for area selection during regional-scale mineral exploration. The Ben Nevis Complex consists of a 3- to 4-km-thick succession of mafic, intermediate and felsic volcanic rocks centered on a small subvolcanic intrusion. Alteration of the volcanic rocks comprises mainly low-temperature assemblages of prehnite, pumpellyite, magnesium-rich chlorite (Fe/Fe+Mg <0.5), iron-rich epidote (>10 wt% Fe ₂O ₃) and calcite. Actinolite ± magnetite alteration occurs proximal to the intrusive core of the complex, but the limited extent of this alteration indicates only local high-temperature fluid circulation adjacent to the intrusion. A distal zone of carbonate alteration is located 4–6 km from the center of the volcano. Although iron-bearing carbonates are present locally within this zone, the absence of siderite argues against a high-temperature origin for this alteration. These observations do not offer positive encouragement for the existence of a fossil geothermal system of sufficient size or intensity to have produced a large massive sulfide deposit.     

Degassing, crystallization and eruption dynamics at Stromboli: trace element and lithium isotopic evidence from 2003 ashes

During its 1800-year-long persistent activity the Stromboli volcano has erupted a highly porphyritic (HP) volatile-poor scoriaceous magma and a low porphyritic (LP) volatile-rich pumiceous magma. The HP magma is erupted during normal Strombolian explosions and lava effusions, while the LP one is related to more energetic paroxysms. During the March–April 2003 explosive activity, Stromboli ejected two typologies of juvenile glassy ashes, namely highly vesicular LP shards and volatile-poor HP shards. Their textural and in situ chemical characteristics are used to unravel mutual relationships between HP and LP magmas, as well as magma dynamics within the shallow plumbing system. The mantle-normalized trace element patterns of both ash types show the typical arc-lava pattern; however, HP glasses possess incompatible element concentrations higher than LP glasses, along with Sr and Eu negative anomalies. HP shards are generally characterized by higher Li contents (to ~20 ppm) and lower δ⁷Li values (+1.2 to −3.8‰) with respect to LP shards (Li contents of 7–14 ppm and δ⁷Li ranging between +4.6 and +0.9‰). Fractional crystallization models based on major and trace element compositions, combined with a degassing model based on open-system Rayleigh distillation and on the assumption that ^melt/fluidD_Li > 1, show that abundant (~30%) plagioclase precipitation and variable degrees of degassing can lead the more primitive LP magma to evolve toward a differentiated (isotopically lighter) HP magma ponding in the upper conduit and undergoing slow continuous degassing-induced crystallization. This study also evidences that in March 2003 Stromboli volcano poured out a small early volume of LP magma that traveled slower within the conduit with respect to later and larger volumes of fast ascending LP magma erupted during the April 5 paroxysm. The different ascent rates and cooling rates of the two LP magma batches (i.e., pre- and post-paroxysm) resulted in small, but detectable, differences in their chemical signatures. Finally, this study highlights the high potential of in situ investigations of juvenile glassy ashes in petrologic and geochemical monitoring the volcanic activity and of Li isotopes as tracers of degassing processes within the shallow plumbing system.     

The chemical composition including the Rare Earth Elements of the three major glass types of Europe and the Orient used in late antiquity and the Middle Ages

Sets of 20 soda ash glasses, 16 soda lime glasses and 23 wood ash glasses mainly from excavations in Europe (additional soda ash glasses from Egypt) were analysed on 61 chemical elements. Average SiO₂ is about 62% in soda glasses and 50% in wood ash glasses. The three groups of glasses contain on average 13% Na₂O, 18% Na₂O and 13% K₂O as fluxes to lower the melting temperature of quartz at their production. The starting materials beside quartz were halophytic plant ash for soda ash glass, trona (Na₃H(CO₃)₂·2H₂O) and lime (clamshells) for soda lime glass and beech ash for wood ash glass. Each of the three major glass types contains specific Rare Earth Element (REE) concentrations mainly contained in quartz and its intergrown minerals. 50 Paleozoic and Mesozoic sandstones from Central Europe represent the quartz composition. The REE pattern of these glasses apparently indicates major compositional stages of the Continental Earth's Crust. The boron to lithium and sodium to potassium ratios as in seawater suggest reactions of materials for soda glass with seawater. Negative Ce anomalies in the three glasses are caused by reactions of quartz with seawater.     

REE and HFS element behaviour in the alteration facies of the Erenler Dağı Volcanics (Konya,Turkey) and kaolinite occurrence

Mainly high-K, calc-alkaline, Late Miocene to Pliocene volcanic rocks cropped out of the Konya area in Central Anatolia, Turkey. The volcanic rocks are predominantly andesitic to dacitic in composition and rarely basalt, basaltic andesite, basaltic trachyandesite and pyroclastics. Kaolinite, illite, Ca-montmorillonite, alunite, jarosite, minamiite and silica polymorphs were formed by widespread and intense hydrothermal alteration in or around the volcanic products. To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, the whole rock chemical composition (major and trace elements, including rare-earth elements (REE) was analysed. The results of the study demonstrate notable differences in the REE behaviour in the different sample groups. REE trends of fresh parent rocks to weakly-, moderately-altered, kaolinitic and alunitic rocks are characterised by strong LREE enrichment ((La/Lu)_cn = 14.57, 11,8 to 15.20, 4.54 to 13.30, 12.5 to 24.2 and 34.6 to 47.26, respectively). Most of the samples have pronounced negative and/or weakly-negative Eu anomalies ranging from 0.75 to 0.98 while three samples have weakly-positive Eu anomalies. LRE element contents are higher than those of HREE in the samples. The LRE elements were strongly enriched in the kaolinitic and alunitic alteration; in weakly- and moderately-altered rocks. LREE are nearly immobile whereas HRE elements show different behaviour in different rock groups. The HFS and TRT elements are slightly mobilised in weakly-altered rocks, but enriched in other alteration types. Elements commonly assumed to be immobile (e.g. Y, Zr, Nb, Hf, TiO₂, Al₂O₃, REE) show variation in mass calculation. LIL elements showed enrichment over LREE and MREE, and similar behaviour, in contrast with HFSE. A clear increment of trans-transition elements (TRTE) was found mainly in alunitic and partly in kaolinitic samples.     

A natural analogue of nuclear waste glass in compacted bentonite

A marine based argillaceous rock containing volcanic glass shards has been investigated to infer the long-term durability of vitrified nuclear waste in compacted bentonite, which is a candidate for buffer material constituting the engineered barrier system for nuclear waste disposal. Fission track ages indicate that the volcanic glass shards, andesitic scoria, have been buried in the argillaceous rock for about 1 Ma. Neither glass matrix dissolution nor precipitation on the surface was seen under an optical microscope. Little leaching of any element has been recognized by analyses using an electron microprobe analyzer. Secondary ion mass spectrometry analysis, however, indicates significant hydration which may dominantly be a permeation of molecular water.As an indicator of durability of glass against groundwater a normalized mass loss of Si (NL_Si) has been evaluated for the volcanic glass based on free energy for hydration. The difference between estimated NL_Si of the volcanic glass and that of a simulated waste glass is within one order so that the volcanic glass may be analogous to a waste glass with respect to durability to water. The argillaceous rock is analogous to the compacted bentonite with respect to physical properties such as dry-density, unconfined compression strength, porosity, and hydraulic conductivity. The ambient physical and chemical conditions surrounding the volcanic glass have been also investigated: temperature was in the range from 4 to 30°C due to the burial history of the volcanic glass. Over most of the past 1 Ma the volcanic glass has been in contact with groundwater originating from seawater. Thermodynamic calculations indicate (1) pH (=7.74–7.94) of the groundwater has mainly been controlled by dissolution of carbonate minerals, (2) the redox potential (Eh=−34–−73 mV) of the groundwater has dominantly been controlled by decomposition of organic materials to produce CH₄(g), and (3) activity of aqueous silica of the groundwater was in equilibrium with SiO₂ amorphous. Because of the equilibrium between aqueous silica and SiO₂ amorphous, the volcanic glass did not dissolve during the burial.Vitrified nuclear waste sealed in compacted bentonite, therefore, will not dissolve significantly if buried in an environment as mentioned above.     

The systematics of chlorine, fluorine, and water in Izu arc front volcanic rocks: Implications for volatile recycling in subduction zones

We studied the systematics of Cl, F and H₂O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ∼400-4000 ppm and F ∼70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (∼6600-8600 ppm) and F (∼780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H₂O of basalt to andesite melt inclusions in plagioclase is estimated to range from ∼2 to ∼10 wt% H₂O. The Izu magmas should be undersaturated in H₂O and the halogens at their preferred levels of crystallization in the middle to lower crust (∼3 to ∼11 kbar, ∼820° to ∼1200°C). A substantial portion of the original H₂O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H₂O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H₂O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94 ± 0.25 wt%, F = 990 ± 270 ppm and H₂O = 25 ± 7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (∼77-129%). Conversely, H₂O (∼13-22% recycled at arc) and F (∼4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H₂O, the calculated percentage of Cl and H₂O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (∼37,000 km), the global arc outflux of fluid-recycled Cl and H₂O at subduction zones amounts to Cl ∼2.9-3.8 × 10¹² g/yr and H₂O ∼0.7-1.0 × 10¹⁴ g/yr, respectively—comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ∼0.3-0.4 × 10¹²g/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H₂O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H₂O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (∼9.5), slab melting will still produce components with low Cl/F ratios (∼0.9), similar to those characteristic of the upper continental crust (Cl/F ∼0.3-0.9).