Petrographic, Chemical and B-Isotopic Insights into the Origin of Tourmaline-Rich Rocks and Boron Recycling in the Martinamor Antiform (Central Iberian Zone, Salamanca, Spain)

Tourmaline in the Martinamor antiform occurs in tourmalinites(rocks with >15–20% tourmaline by volume), clasticmetasedimentary rocks of the Upper Proterozoic Monterrubio formation,quartz veins, pre-Variscan orthogneisses and Variscan graniticrocks. Petrographic observations, back-scattered electron (BSE)images, and microprobe data document a multistaged developmentof tourmaline. Overall, variations in the Mg/(Mg + Fe) ratiosdecrease from tourmalinites (0·36–0·75),through veins (0·38–0·66) to granitic rocks(0·23–0·46), whereas Al increases in thesame order from 5·84–6·65 to 6·22–6·88apfu. The incorporation of Al into tourmaline is consistentwith combinations of ^xAl(NaR)_–1 and AlO(R(OH))_–1exchange vectors, where ^x represents X-site vacancy and R is(Mg + Fe²⁺ + Mn). Variations in ^x/(^x + Na) ratios are similarin all the types of tourmaline occurrences, from 0·10to 0·53, with low Ca-contents (mostly <0·10apfu). Based on field and textural criteria, two groups of tourmaline-richrocks are distinguished: (1) pre-Variscan tourmalinites (probablyCadomian), affected by both deformation and regional metamorphismduring the Variscan orogeny; (2) tourmalinites related to thesynkinematic granitic complex of Martinamor. Textural and geochemicaldata are consistent with a psammopelitic parentage for the protolithof the tourmalinites. Boron isotope analyses of tourmaline havea total range of ¹¹B values from –15·6 to 6·8;the lowest corresponding to granitic tourmalines (–15·6to –11·7) and the highest to veins (1·9to 6·8). Tourmalines from tourmalinites have intermediate¹¹B values of –8·0 to +2·0. The observedvariations in ¹¹B support an important crustal recycling ofboron in the Martinamor area, in which pre-Variscan tourmaliniteswere remobilized by a combination of mechanical and chemicalprocesses during Variscan deformation, metamorphism and anatexis,leading to the formation of multiple tourmaline-bearing veinsand a new stage of boron metasomatism. KEY WORDS: tourmalinites; metamorphic and granitic rocks; mineral chemistry; whole-rock chemistry; boron isotopes     

ROCKS & MINERALS DETERMINATION AND ANALYSIS

正20141456 Chen Juan(Laboratory of High Temperature and High Pressure Study of the Earth’s Interior,Institute of Geochemistry,Chinese Academy of Sciences,Guiyang550002,China);Tang Hongfeng Progress in Analytical Methods of Tungsten Isotope and Experimental Research on Digestion of Whole     

Study of physical and chemical properties of vitrinites. Inferences on depositional and coalification controls

A detailed study of petrological, geochemical, textural and coking properties was carried out on vitrains from the Puertollano, Blanzy–Montçeau, Asturias and Teruel. The objective was to determine in depth the physical and chemical properties of a series of natural and pure vitrinites of different rank, and the influence that the sedimentary and post-sedimentary conditions had on them. It is demonstrated that although vitrains are almost entirely made up of the huminite/vitrinite maceral group they have a different composition, thermal behaviour and physical properties. Thus, geochemical and textural properties of Blanzy–Montçeau vitrains can be considered to be representative of the telinite, the major component in both samples (75% vol.) at the beginning of the bituminization stage (subbituminous/high volatile C bituminous coals). The characteristics of the Puertollano vitrains described here can also be attributed to the telocollinite (>80% vol.) for the high volatile C bituminous coal. Variations in physico-chemical properties between Puertollano and Blanzy–Montçeau vitrains are due to the differences in the initial composition of organic matter. Slight differences (i.e., bed moisture content or porosity) between vitrains from the two coal seams in the same basin can be attributed to their stratigraphic position. Several parameters such as S₂, HI, oil and extraction yield and fluorescent properties suggest that the Puertollano and Blanzy–Montçeau vitrains have a lower hydrocarbon potential. The relationships between geochemical and textural properties make it possible to distinguish between ‘normal' and perhydrous vitrains. The two different hydrogen-enrichment processes that occur in vitrains from the Teruel and Asturias basins can be distinguished from the extraction yield data.     

Surfactant components of marine organic matter as agents for biogeochemical fractionation and pollutant transport via marine aerosols

The role of surfactant organic matter in marine aerosol production has been studied under conditions in which there is a large coverage of whitecaps on the sea surface. To improve the knowledge of matter exchange and pollutant recycling from the sea surface into the atmosphere, a spray drop adsorption model (SDAM) was developed and the validity of the proposed model verified by the following experimental results: (1) an increase of surfactant matter on the sea surface during rough sea conditions (‘surface wave concentration'); (2) an (hyperbolic-like) increase of the enrichment ratio (ER) of surfactant fluorescent organic matter (SFOM), made up predominantly by humic substances (HS), as the particle size decrease; (3) a similar behaviour for elements with pollutant properties, and which are known to interact with HS and other surfactant materials, considered pollution tracers. An additional laboratory experiment, based on the adsorption model conditions, gives enrichment ratio greater than unity for K and Ca. The first results on marine aerosols trapped in marine clouds (at 1000 m above sea level and at 100 km from the coast) seem to further support the proposed model and its ability to predict the transition from saline to almost entirely organic particles for the smaller fractions of marine aerosols. The possible contribution of these particles to the recycling and to the long range transport of pollutants via marine aerosols has been considered.     

Peptide decomposition by extracellular hydrolysis in coastal seawater and salt marsh sediment

Extracellular peptide hydrolysis rates were measured in seawater and sediment from Flax Pond salt marsh using peptide analogs (LYA-peptides) as substrates. This technique allows the direct measurement of specific hydrolysis products and thus provides insights into enzymatic hydrolysis pathways. In sediments, hydrolysis rate constants of LYA-peptides varied seasonally and with depth. Highest activity was found in spring and summer, and most cores exhibited a subsurface maximum. Calculations using the concentrations of chemically-measured peptides suggested that extracellular hydrolysis of peptides is faster than the rate of free amino acids uptake. However, not all peptides may be available for enzymatic hydrolysis. In both seawater and sediment, extracellular hydrolysis of peptides of up to 8 amino acids yielded smaller peptides and free amino acids. Hydrolysis rates depended on size of the peptide substrate, although a clear relationship with number of amino acid constituents was not evident. Peptides containing >2 amino acids were hydrolyzed 10–400 times faster than dipeptides or the fluorogenic substrate Leucine-MCA. Thus, dipeptidases are either uncommon in nature, or hydrolysis is carried out by nonspecific hydrolases that with a low affinity for dipeptides. This is also suggested by the presence of a lag time before dipeptide hydrolysis begins, and the absence of dipeptide hydrolysis in 0.2-μm-filtered. One implication of this finding is that measurements of hydrolysis rates using substrates like Leu-MCA may not accurately predict the magnitude of hydrolysis rates of macromolecules in the marine environment. Even though dipeptide hydrolysis is slow compared to that of larger peptides, LYA-dipeptides are preferentially produced from the hydrolysis of larger substrates. LYA-dipeptides do not penetrate cell membranes of microorganisms because of their size, but natural dipeptides are smaller and can be transported across the cell membrane. Since dipeptides do not appear to accumulate in natural waters, they must be rapidly removed by microorganisms.     

Heavy metals in particulate matter and sediments in the southern Barcelona sedimentation system (North-western Mediterranean)

Concentrations of selected heavy metals (Cr, Cu, Ni, Pb and Zn) from surface sediments, suspended particulate matter and settling particles in the southern Barcelona continental margin were studied in order to evaluate the environmental impact of the anthropogenic metals discharged by the Llobregat River in this Mediterranean area. The temporal variation of heavy metals discharged by this river onto the continental shelf is clearly related to the river water flow. Part of the fine sediment and associated heavy metals transported by the Llobregat River during periods of low river flow accumulate on the river bed, and they are totally removed and discharged onto the Barcelona continental shelf during sporadic river water flow increases. Metals produce significant anomalies of chromium (×2.5), copper (×3.4) and zinc (×3.7) in the surface sediments of the Llobregat prodelta and tend to be transported along the continental shelf following the mean flow. Metals associated with the finest suspended flocs transferred to the slope are controlled by the shelf-slope density front and are transported along slope by the general geostrophic current, instead of accumulating and becoming concentrated in the slope bottom sediments. Settling particulate matter collected in sediment traps on the Barcelona continental slope offshore of the shelf-slope front shows low heavy metal concentrations except in a few sediment trap samples that are significantly metal-enriched in chromium (×4.5) and zinc (×6.8). This enrichment is associated with very short and sporadic river flow increases and is only recorded inside the Foix submarine canyon, which acts as a preferential conduit for the shelf-slope sediment transfer.     

低压密闭消解-电感耦合等离子体发射光谱法测定地质样品中的硼

采用酸溶-电感耦合等离子体发射光谱法(ICP-OES)测定地质样品中的全硼量,关键环节在于如何防止样品消解过程中硼元素的损失,降低测量过程中的基体干扰、光谱干扰和记忆效应。基于以上问题,本文采用氢氟酸-硝酸-高氯酸-磷酸在低压密闭溶样罐中消解样品,溶出的硼元素与少量磷酸充分络合,防止硼的挥发损失;以基体及主成分浓度与样品相类似的地质类固体标准物质绘制标准曲线做线性校准,有效匹配和降低样品的基体干扰;采用仪器自带的操作软件,观察分析谱线附近是否存在其他元素的干扰,来确定背景扣除最佳的位置及宽度,降低ICP-OES测量中的光谱干扰;以10%的王水作为进样系统的冲洗液,有效消减测量过程中的记忆效应。当稀释因子为200时,方法的检出限(3SD)为1.2μg/g,定量限(10SD)为4.0μg/g;用岩石、土壤及水系沉积物国家一级标准物质对精密度及准确度进行分析验证,11次测定相对标准偏差为1.8%～7.9%,相对误差为-3.6%～6.3%;以外检分析结果为参考,对硼含量在定量限以上的样品测定,相对误差为-9.3%～12.5%。     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

浮游有孔虫个体大小对硼同位素分析的影响

对比分析了太平洋(Site 806)、大西洋(Site 664)和加勒比海地区(Site 999)末次冰期最盛期和全新世钻孔顶部不同尺寸大小的浮游有孔虫Globigerinoides sacculifer(500～600μm和300～355μm)和Globi-gerinoides ruber(300～355μm和250～300μm)的硼同位素组分变化,发现个体相对较小的有孔虫样品由于受到样品量以及样品前处理过程的影响,其硼同位素在末次冰期最盛期出现异常,浮游有孔虫硼同位素分析,尤其是冰期-间冰期时间尺度上的硼同位素分析,适合用个体相对较大的有孔虫。末次冰期最盛期太平洋和加勒比海地区溶解作用可能加强,其G.sacculifer的硼同位素偏低,但G.ruber的硼同位素不受溶解作用的影响,能够反映末次冰期海水pH值的变化。三个钻孔末次冰期最盛期G.ruber的硼同位素比全新世的硼同位素平均高(1.3±1.2)‰(2s.e.),与理论预测值1.6‰一致。     

老挝甘蒙省钾镁盐矿床中微量硼矿物的鉴定和准确定名

以老挝甘蒙省钾镁盐矿床ZK318钻孔的含矿段(下盐层)为研究对象,对其开展了微量硼矿物的鉴定研究工作,以完善矿床的矿物组合类型。全岩样品的XRD初步结果给出,在顶部钾盐岩层中含有少量方硼石。为了进一步全面鉴定硼矿物的种类,对全岩样品溶解后得到的不溶物多晶集合体进行XRD分析,结果表明,不溶物中的硼矿物主要为方硼石(55%),其次为三斜晶系3A型氯硼钙石(15%)。3A型氯硼钙石在全岩样品中的含量不足1%,属微量矿物,因低于XRD的检出限,故在全岩样品的XRD图谱中无该矿物的衍射峰出现。此外,对三斜晶系3A型氯硼钙石的中文准确命名进行了讨论,指出中文定名应与国际惯例一致,即废除副水氯硼钙石(parahilgardite)一词,定名为3A型氯硼钙石(hilgardite-3A)以体现结构的微细差别,同时达到中文命名规范统一的目的。因此,该矿床中的硼矿物为少量方硼石和微量3A型氯硼钙石。