土壤腐殖质提取和分组综述

土壤腐殖质的定量提取、分离与纯化是深入研究土壤腐殖质的重要前提。本文详细综述了国内外腐殖质提取和分组的实验手段和研究进展;以国际腐殖质协会提供的标准方法为参考,对比论述了提取剂种类,提取次数、提取剂用量等的选择;对比讨论了两种主要的土壤腐殖质的分组方法。超滤分离和体积排阻色谱是腐殖质物理化学表征研究中的两种新兴技术,笔者认为组合使用两种实验手段对土壤腐殖质进行细致的分离与分组研究有助于深化理解土壤腐殖质的化学性质和分子结构。     

Humic Ion-Binding Model VI: An Improved Description of the Interactions of Protons and Metal Ions with Humic Substances

Humic Ion-Binding Model VI, a discrete site/electrostatic model of the interactions of protons and metals with fulvic and humic acids, is applied to 19 sets of published data for proton binding, and 110 sets for metal binding. Proton binding is described with a site density, two median intrinsic equilibrium constants, two parameters defining the spread of equilibrium constants around the medians, and an electrostatic constant. Intrinsic equilibrium constants for metal binding are defined by two median constants, log K_MA and log K_MB, which refer to carboxyl and weaker-acid sites respectively, together with a parameter, LK₁, defining the spreads of values around the medians. A further parameter, LK₂, takes account of small numbers of strong binding sites. By considering results from many data sets, a universal average value of LK₁ is obtained, and a correlation established between log K_MB and log K_MA. In addition, a relation between LK₂ and the equilibrium constant for metal-NH₃ complexation is tentatively suggested. As a result, metal-binding data can be fitted by the adjustment of a single parameter, log K_MA. Values of log K_MA are derived for 22 metal species. Model VI accounts for competition and ionic strength effects, and for proton-metal exchange.     

水环境中腐殖质对重金属吸附行为的影响

水环境中金属离子-腐殖质-矿物（或细菌）之间的相互作用能够显影响金属离子在地质体中的迁移和归宿。本综述了水环境中腐殖质对金属离子在矿物、微生物等表面只附行为影响的研究现状，分析讨论了复合型表面的基本特点、腐殖质对金属吸附到矿物表面的影响因素、腐殖质影响细菌表面吸附金属离子的机理，以及对三相体系不同研究的研究思路与结论等。     

分子荧光偏振技术及其在研究腐殖物质与污染物相互作用方面的研究进展

腐殖物质对污染物如有毒金属元素(如汞．铜和铅等)及有机污分子荧光染物(如多环芳烃,有下几农药等)具有络合或吸附作用,从而改变污染物的存在形式及其迁侈途径．所以能有效地降低污染物的毒性。近年来,用分子荧光学研究两者间的这种作用过程逐渐得到人们的关注。本文综述了运用荧光偏振技术在腐殖物质与污染物的相互作用领域的研究现状。荧光偏振的研究成果可加深对腐殖物质与污染机理的认识．能较精确地定量评估它们之间的作用强度．了解它们结合后的分子构型变化．有助于了解污染物在环境中的生物地球化学循环。     

黑色页岩微量元素形态分析及地质意义

本文采用 4级不同形态逐级提取的方法研究了湘西上震旦统、下寒武统黑色页岩微量元素的物相分布特点。各形态微量元素含量和主要矿物电子探针分析结果表明 ,微量元素主要受控于有机质和硫化物含量的变化 ,较高的有机产率和缺氧的古海洋环境是影响黑色页岩中微量元素分布的决定因素。     

Noble metals in black shales of the Sukhoi Log gold deposit (East Siberia): evidence from scintillation arc atomic-emission spectrometry

Scintillation arc atomic-emission spectrometry (SAES) is used to study noble metals (NM), including Au, Ag, Pt, Pd, Ir, Os, Rh, and Ru, in black shales of the Sukhoi Log gold deposit (Irkutsk Region, Russia), with a focus on NM total contents in samples and on the compositions and sizes of NM-bearing particles. The estimated sizes of gold particles and their distribution are confirmed by results of scanning electron microscopy combined with energy dispersive X-ray microanalysis (SEM-EDX). The SAES results are in satisfactory agreement with earlier SEM-EDX data on NM species but reveal a much greater number and diversity of element associations.     

浙江中部典型黑色岩系分布区土壤-作物富硒特征与重金属风险评价

富硒土地是生产富硒农产品的宝贵资源,黑色岩系形成的土壤通常富含硒和重金属元素。为了指导这类富硒土地资源的安全开发利用,选择浙江中部典型黑色岩系分布区,通过调查土壤-作物中硒和重金属的浓度及生物有效性,评价农产品富硒率,识别作物重金属超标风险。结果显示:研究区富硒土壤占38%,足硒土壤占62%,水稻和莲子富硒率分别为85.71%和100%;受黑色岩系风化成土影响,研究区土壤镉含量介于污染筛选值和风险管控值之间的样品比例为26%,且Cd活动态和潜在活动态所占比例分别为57%和40%,水稻籽实中Cd超标率为31%,莲子Cd含量均不超标。基于土壤重金属总量和形态的风险评价表明,富硒土壤开发利用的风险区主要位于西皮山岗和腰塘边一带,建议禁止种植农产品,其他黑色岩系发育的富硒丘陵地区,虽然土壤镉含量较高,但因土壤Cd的生物有效性和水稻中Cd的超标率较低,应加以保护和合理开发利用。     

Geochemical and Geological Characterization of Marine-Continental Transitional Shale: A Case Study in the Ordos Basin, NW China

The organic-rich shale of the Shanxi and Taiyuan Formation of the Lower Permian deposited in a marine-continental transitional environment are well developed in the Ordos Basin, NW China, which is considered to contain a large amount of shale hydrocarbon resources. This study takes the Lower Permian Shanxi and Taiyuan shale collected from well SL# in the Ordos Basin, NW China as an example to characterize the transitional shale reservoir. Based on organic geochemistry data, X-ray diffraction (XRD) analysis, field-emission scanning electron microscopy (FE-SEM) observations, the desorbed gas contents of this transitional shale were systematically studied and the shale gas potential was investigated. The results indicate that the Lower Permian Shanxi and Taiyuan shale has a relatively high total organic carbon (TOC) (average TOC of 4.9%) and contains type III kerogen with a high mature to over mature status. XRD analyses show that an important characteristic of the shale is that clay and brittle minerals of detrital origin comprise the major mineral composition of the marine-continental transitional shale samples, while the percentages of carbonate minerals, pyrite and siderite are relatively small. FE-SEM observations reveal that the mineral matrix pores are the most abundant in the Lower Permian shale samples, while organic matter (OM) pores are rarely developed. Experimental analysis suggests that the mineral compositions mainly govern the macropore development in the marine-continental transitional shale, and mineral matrix pores and microfractures are considered to provide space for gas storage and migration. In addition, the desorption experiments demonstrated that the marine-continental transitional shale in the Ordos Basin has a significantly potential for shale gas exploration, ranging from 0.53 to 2.86 m3/t with an average value of 1.25m3/t, which is in close proximity to those of terrestrial shale (1.29 m3/t) and marine shale (1.28 m3/t). In summary, these results demonstrated that the Lower Permian marine-continental transitional shale in the Ordos Basin has a significantly potential for shale gas exploration.     

Happy Jack Uraninite: A New Reference Material for High Spatial Resolution Analysis of U‐Rich Matrices

There is currently a lack of well‐characterised matrix‐matched reference materials (RMs) for forensic analysis of U‐rich materials at high spatial resolution. This study reports a detailed characterisation of uraninite (nominally UO_2+x) from the Happy Jack Mine (UT, USA). The Happy Jack uraninite can be used as a RM for the determination of rare earth element (REE) mass fractions in nuclear materials, which provide critical information for source attribution purposes. This investigation includes powder X‐ray diffraction (pXRD) data, as well as major, minor and trace element abundances determined using a variety of micro‐analytical techniques. The chemical signature of the uraninite was investigated at the macro (cm)‐scale with micro‐X‐ray fluorescence (µXRF) mapping and at high spatial resolution (tens of micrometre scale) using electron probe microanalysis (EPMA) and laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analyses. Based on EPMA results, the uraninite is characterised by homogeneous UO₂ and CaO contents of 91.57 ± 1.49% m/m (2s uncertainty) and 2.70 ± 0.38% m/m (2s), respectively. Therefore, CaO abundances were used as the internal standard when conducting LA‐ICP‐MS analyses. Overall, the major element and REE compositions are homogeneous at both the centimetre and micrometre scales, allowing this material to be used as a RM for high spatial resolution analysis of U‐rich samples.     

中性盐溶液提取土壤中金属活动态及其对隐伏矿的指示: 以甲基卡稀有金属矿区为例

以甲基卡稀有金属矿区X03 号超大型稀有金属矿体以及804 号脉等两个典型隐伏矿体作为研究对象,采用硫酸钾 （K2SO4） 中性盐溶液作为金属活动态提取剂,进行了土壤中Li 元素活动态的提取试验。结果表明,Li 元素活动态的地球化 学异常很好地对应了隐伏矿体的位置,能够有效地指示隐伏矿体的存在。在甲基卡土壤中目标元素内生组分/外生组分比值 很高的稀有金属矿区,采用中性盐溶液这类弱提取剂,才能最大程度地排除土壤内生组分的干扰,有效识别隐伏矿体。通 过提取条件优化实验,在甲基卡地区采用硫酸钾（K2SO4） 溶液提取土壤中Li 元素活动态的最佳技术参数为：提取剂浓度 0.2 mol/L,粒级200 目,pH为6.82,固液比为1:5,提取时间为48 h。     

Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

Rapid Determination of Trace and Ultra Trace Level Elements in Diverse Silicate Rocks in Pressed Powder Pellet Targets by LA‐ICP‐MS using a Matrix‐Independent Protocol

A simple, single sample preparation involving pressed rock powder pellets was utilised to determine the trace and ultra trace abundances of petrogenetically important elements including high field‐strength elements and REEs by laser ablation‐ICP‐MS. One of the elements predetermined by XRF spectrometry served as an internal standard. The influence of sample preparation parameters (grain size, pellet compactness and amount of binding media) on analytical performance was also investigated, including sample homogeneity issues at the laser sampling scale. Line scanning with a high repetition frequency (20 Hz) and large beam diameter (200 μm) ensured ablation from a larger sample surface area, eliminating issues related to sample heterogeneity. A median grain size of about 10 μm for silicate rock powders was found to be sufficiently representative at this scale of laser sampling. Granitic rocks or samples containing resistant minerals such as zircon needed extra grinding to achieve grain sizes down to < 5 μm for better precision for elements that are concentrated in these phases. Using ¹³⁷Ba as an internal standard, reasonable accuracies within 15–20% for most of the high mass trace elements were achieved; in the case of low mass elements, it may deviate up to 40%. Precision of measurements rarely exceeded 15% RSD.     

An Acetic Acid‐Based Extraction Protocol for the Recovery of U,Th and Pb from Calcium Carbonates for U‐(Th)‐Pb Geochronology

A new method for the simultaneous recovery of U, Th and Pb from ca. 0.5 g calcium carbonate samples for the purpose of U‐(Th)‐Pb geochronometry is presented. The protocol employs ion‐exchange chromatography. Standard anion exchange resin (AG 1‐X8 100–200 mesh) was used as the static phase, and 90% acetic acid was used as the mobile phase to elute the unwanted matrix components; dilute nitric acid was used to elute the U, Th and Pb. Blanks of 1.8 pg Th, 6.4 pg Pb and 8.4 pg U were obtained. The protocol was evaluated by determining the isotopic composition of U‐Th‐Pb separates obtained from an in‐house reference material (prepared from a natural speleothem) by MC‐ICP‐MS. An independently dated speleothem was also reanalysed. Based on these tests, the extraction protocol had an acceptable blank and produced a Pb separate sufficiently free of matrix‐induced instrumental biases to be appropriate for U‐Th‐Pb chronology.     

Multiple Sources of Metals of Mineralization in Lower Cambrian Black Shales of South China: Evidence from Geochemical and Petrographic Study

Black shales of the Lower Cambrian Niutitang Formation in southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province) host regionally distributed stratiform polymetallic Ni‐Mo‐platinum group elements (PGE)‐Au phosphate‐ and sulfide‐rich ores. These are confined to a ≥0.2‐m thick ore horizon composed of mineralized bodies of algal onkolites, phosphate nodules, and sulfide and shale clasts in a mineralized phosphate‐ and organic matter‐rich matrix. Compared to footwall and hanging wall shales, the ore bed is strongly enriched in Ni (up to 100‐fold), As (up to 97‐fold), Mo (up to 95‐fold), Sb (up to 67‐fold), Rh (up to 49‐fold), Cu (up to 37‐fold), Pd (up to 33‐fold), Ru (up to 24‐fold), Zn (up to 23‐fold), Pt (up to 21‐fold), Ir (up to 15‐fold), Co (up to 14‐fold), and Pb (up to 13‐fold). Even footwall and hanging wall black shales are significantly enriched by Mo (21‐fold) and Ni (12‐fold) but depleted in Cr in comparison to average Cambrian black shale. Organic matter is represented by separate accumulations dispersed in the rock matrix or as biotic bitumen droplets and veinlets in ore clasts. Similar organic carbon (C_org) values in an ore bed and enclosing footwall and hanging wall shales of little mineralization indicate that metal accumulation was not controlled only by biogenic productivity and organic matter accumulation rate. Evaporitic conditions during sedimentation of the basal part of the Niutitang Formation were documented by an occurrence of preserved Ni‐, V‐, Cr‐, and Cu‐enriched phosphate‐rich hardground with halite and anhydrite pseudomorphs on the paleosurface of the underlying Neoproterozoic carbonates. Neoproterozoic black shales of the Doushantuo Formation are characterized by increased metal concentrations. Comparison of metal abundances in both hardground and Doushantuo black shales indicate that black shales could have become a source of metal‐rich hardground during weathering. The polymetallic Ni‐Mo‐PGE sulfide‐rich ore bed is interpreted to represent a remnant of shallow‐water hardground horizon rich in metals, which originated in a sediment‐starved, semi‐restricted, seawater environment. During the Early Cambrian transgression an influx of fresh seawater and intensive evaporation, together with the hydrothermal enrichment of seawater in a semi‐restricted basin, resulted in the formation of dense metalliferous brines; co‐precipitation of metals together with phosphates and sulfides occurred at or above the oxic–anoxic sediment interface. Metal‐enriched hardground was disintegrated by the action of waves or bottom currents and deposited in a deeper part of the anoxic basin. Contemporaneously with the formation of a polymetallic Ni‐Mo‐PGE‐Au sulfide ore bed, economic sedimentary exhalative (SEDEX)‐type barite deposits were forming in a stratigraphically and geotectonically similar setting. The results of geochemical study at the Shang Gongtang SEDEX‐type Ba deposit indicate that concentrations of Ag, As, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, Zn and other metals decrease from top of the barite body toward the hanging wall black shale. Lower Cambrian black shales of the Niutitang Formation above the barite body also display similar element abundances as Neoproterozoic black shales of the Doushantuo Formation, developed in the footwall of the barite body. But the geochemical composition of the sulfide layer is different from the Ni‐Mo ore bed, showing only elevated Pb, Cu, Ni and Mo values. It is suggested that hydrothermal brines at Shang Gongtang might have leached metals from footwall Neoproterozoic sequences and became, after mixing with normal seawater, an additional source of Ag, Cr, Cu, Pb, Sb, Zn, Ni, PGE, V and other metals.     

A Flux‐Free Fusion Technique for Rapid Determination of Major and Trace Elements in Silicate Rocks by LA‐ICP‐MS

A simple flux‐free fusion technique was developed to analyse major and trace element compositions of silicate rocks. The sample powders were melted in a molybdenum capsule sealed in a graphite tube to make a homogenous glass in a temperature‐controlled one‐atmosphere furnace. The glass was then measured for both major and trace element concentrations by LA‐ICP‐MS using a calibration strategy of total metal‐oxide normalisation. The optimum conditions (i.e., temperature and duration) to make homogeneous glasses were obtained by performing melting experiments using a series of USGS reference materials including BCR‐2, BIR‐1, BHVO‐2, AGV‐1, AGV‐2, RGM‐1, W‐2 and GSP‐2 with SiO₂ contents from 47 to 73% m/m. Analytical results of the USGS reference materials using our method were generally consistent with the recommended values within a discrepancy of 5–10% for most elements. The routine precision of our method was generally better than 5–10% RSD. Compared with previous methods of LA‐ICP‐MS whole‐rock analyses, our flux‐free fusion method is convenient and efficient in making silicate powder into homogeneous glass. Furthermore, it limits contamination and loss of volatile elements during heating. Therefore, our new method has great potential to provide reliable and rapid determinations of major and trace element compositions for silicate rocks.     

Magma Origin and Evolution of Tengchong Cenozoic Volcanic Rocks from West Yunnan,China: Evidence from Whole Rock Geochemistry and Nd‐Sr‐Pb Isotopes

Tengchong Cenozoic volcanics that have record key information on the tectonic evolution and mantle features of the southeast margin of the Tibetan Plateau are of great importance because of its unique eruption history spanning the entire Quaternary period. Magma origin and evolution of Tengchong Cenozoic volcanic rocks were studied on the basis of Nd-Sr-Pb isotope and major and trace element data from different eruptions in the Ma’anshan area. Different samples within one eruption show relative identical lithologies, chemical and isotopic compositions. However, the geochemical features for the five eruptions are distinct from each other. These volcanic rocks show low Mg# values (<45), moderate to high fractionation of LREEs and HREEs, and enrichment of Pb and Ba and depletion of Nb. Tengchong Cenozoic volcanic rocks were derived from an enriched mantle based on Nd-Sr-Pb isotopic studies. And lines of evidence show that crustal contamination should be involved before the eruption of different periods of Tengchong Cenozoic volcanic rocks. Older subducted components may be responsible for adakite recycling at various stages of evolution, which results in the origin of the enriched mantle source magma accounting for the isotopic features of Tengchong Cenozoic volcanic rocks. Segregated primitive magma pulsating injected into magma chamber, fractional crystallized and contaminated with crust component. Finally, magmas with distinct chemical and isotopic compositions for each eruption formed. The extension of the northeast segment of the Yingjiang tectonic belt triggered the pulsating eruption of the Cenozoic volcanics in the Tengchong area.     

黑矿型矿床成矿物质来源：日本上向黑矿铼—锇和氦同位素证据

上向黑矿（Uwamuki Kuroko)是日本最典型的黑矿型矿床，它形成于日本岛弧中新世矢折岛弧裂谷环境，产于双峰式岩石组合的长英质火山岩系中。矿床由下部筒状硅矿带和上部块状黑矿带构成，后者显示典型的上黑（黑矿）下黄（黄矿）金属分带。为探索研究长期争议的成矿物质来源，系统测定了矿石和主岩的Os,He同位素组成。含矿流纹岩系的R／RA值介于0．93－1．14间，证实该岩浆可能主要来源于陆壳重熔。上向黑矿的上部块状黑矿矿石具较高的^187Os/^188Os值（2．246－7．608），反映矿石Os主体来源于壳源沉积物或矿区基底岩系；下部脉状－网脉状硅矿、块状黄矿和少量黑矿则具低^187Os/^188Os值（0．423－0．793），证实矿石Os具两源性，估计幔源物质贡献约57％－89％，壳源物质贡献约11％－43％。此外，在上部块状黑矿带内部，矿石 ^187Os/^188O显示清楚的垂向韵律性变化，揭示了成矿流体及成矿物质的周期性混合，据此，本文提出了一个新的两阶段成矿模式。     

A Quantitative Evaluation of Shale Gas Content in Different Occurrence States of the Longmaxi Formation: A New Insight from Well JY-A in the Fuling Shale Gas Field,Sichuan Basin

Comprehensive quantitative evaluation of shale gas content and the controlling factors in different occurrence states is of great significance for accurately assessing gas-bearing capacity and providing effective well-production strategies. A total of 122 core samples from well JY-A in the Fuling shale gas field were studied to reveal the characteristics of S_1 l shale,15 of which were selected to further predict the shale gas content in different occurrence states, which are dependent on geological factors in the thermal evolution process. Geological parameters were researched by a number of laboratory programs, and the factors influential in controlling shale gas content were extracted by both PCA and GRA methods and prediction models were confirmed by the BE method using SPSS software. Results reveal that the adsorbed gas content is mainly controlled by TOC, Ro, SSA, PD and pyrite content, and the free gas content is mainly controlled by S_2, quartz content, gas saturation and formation pressure for S_1 l in well JY-A. Three methods, including the on-site gas desorption method, the empirical formula method, and the multiple regression analysis method were used in combination to evaluate the shale gas capacity of well JY-A, all of which show that the overall shale gas content of well JY-A is in the range of 2.0–5.0 m~3/t and that the free gas ratio is about 50%, lower than that of well JY-1. Cause analysis further confirms the tectonics and preservation conditions of S_1 l in the geological processes, especially the influence of eastern boundary faults on well JY-A, as the fundamental reasons for the differences in shale gas enrichment in the Jiaoshiba area.     

New Evidence for Hydrothermal Sedimentary Genesis of the Ni‐Mo Deposits in Black Rock Series of the Basal Cambrian,Guizhou Province: Discovery of Coarse‐Grained Limestones and its Geochemical Characteristics

The molybdenum-nickel deposits in Shuidong District of Nayong County (Guizhou Province, Southwest China) are found mainly in black shale series of Lower Cambrian Niutitang Formation, which is another Mo-Ni-rich region besides Zunyi District (Guizhou province). Our systematic study on the Mo-Ni deposits in Tangjiaba of Nayong reveals that layered coarse-grained limestones, spherical beaded limestones concretions are hosted at the lower seam of the Mo-Ni deposits. Its strong negative carbon isotope anomaly (the carbon isotope value of the coarse-grained limestones varies from ?2.148‰ to 8.223‰) is similar to that in the modern submarine black smoker chimney. The carbon in the coarse-grained limestones from black rock series of Nayong County might be deep source inorganic carbon. The seams, coarse-grained limestones, ore-bearing coarse-grained limestones and the roof and floor of the deposits are characterized by co-variation on the trace element spider diagram, showing good homology. The extraordinary enrichment of Ag, As and Sb resembles hydrothermal sedimentation. Pro-Earth's core elements Se is strongly enriched in Ni-Mo ore-bearing coarse-grained limestones. The ore-bearing rock series has an extremely low Th/U value (0.012–0.19); in the logU-logTh Cartesian Coordinates, the samples of the roof and floor of the deposits and ore-bearing coarse-grained limestones are found in the East Pacific tise; and the samples of coarse-grained limestones are found between the paleo-hydrothermal dedimentary area and the East Pacific tise. The chondrite-normalized rare earth element patterns of the Ni-Mo deposits show LREE enrichment, Ce negative anomaly, and Eu negative anomaly (which is supposed to be influenced by the deep magmatic processes in an extensional environment) resembles the rare earth element distribution patterns of the fluid and its sediments in modern submarine hydrothermal system. It proves that coarse-grained limestones is characterized by typical hydrothermal limestones, being closely related with the genesis of Mo-Ni deposits in Nayong County, which provides new evidence for hydrothermal sedimentary genesis of Mo-Ni deposit and negative carbon anomaly in the basal Cambrian on a global scale.     

A New LA‐ICP‐MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti‐in‐quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining ⁴⁸Ti mass fractions in quartz by LA‐ICP‐MS at the 1 μg g^?1 level, relevant to quartz in HP‐LT terranes. We suggest that natural quartz such as the low‐CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g^?1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of ⁴⁸Ti as a normalising mass. Average titanium mass fraction from thirty‐three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g^?1 (2s) using ⁴⁸Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of ⁴⁸Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using ⁴⁹Ti as an analyte.