大气中溴的环境地球化学研究进展

溴是大气平流层和对流层中的重要物种,能参与大气中的多种化学过程,对臭氧的损耗影响很大,同时也干扰大气的硫循环和汞循环,在大气化学中起着十分重要的作用.综述了近年来大气对流层和平流层溴的种类和含量、自然来源和人为来源,以及化学性质,并重点总结了活性溴物种BrO在大气中的存在情况及其在臭氧损耗中的作用.最后,提出了目前大气...     

Trace element degassing and enrichment in the eruptive plume of the 2000 eruption of Hekla volcano, Iceland

During its last eruption in February 2000, Hekla volcano (Iceland) emitted a sub-Plinian plume that was condensed and scavenged down to the ground by heavy snowstorms, offering the unique opportunity to study the chemistry of the gaseous plume released during highly explosive eruptions. In this paper, we present results on trace element and minor volatile species (sulfates, chlorides, and fluorides) concentrations in snow samples collected shortly after the beginning of the eruption. The goal of this study is to better constrain the degassing and mobility of trace elements in gaseous emissions. Trace element volatility at Hekla is quantified by means of enrichment factors (EF) relative to Be. Well-known volatile trace elements (e.g., transition metals, heavy metals, and metalloids) are considerably enriched in the volcanic plume of Hekla. Their abundances are governed by the primary magmatic degassing of sulfate and/or halide compounds, which are gaseous at magmatic temperature. Their volatility is, however, slightly lower than in basaltic systems, most likely because of the lower magma temperature and higher magma viscosity at Hekla. More surprisingly, refractory elements (e.g., REE, Th, Ba, and Y) are also significantly enriched in the eruptive plume of Hekla where their apparent volatility is two orders of magnitude higher than in mafic systems. In addition, REE patterns normalized to the Hekla 2000 lava composition show a significant enrichment of HREE over LREE, suggesting the presence of REE fluorides in the volcanic plume. Such enrichments in the most refractory elements and REE fractionation are difficult to reconcile with primary degassing processes, since REE fluorides are not gaseous at magma temperature. REE enrichments at Hekla could be attributed to incongruent dissolution of tephra grains at low temperature by F-rich volcanic gases and aerosols within the eruptive plume. This view is supported by both leaching experiments performed on Hekla tephra and thermodynamic considerations on REE mobility in hydrothermal fluids and modeling of glass dissolution in F-rich aqueous solutions. Tephra dissolution may also explain the observed enrichments in other refractory elements (e.g., Th, Y, and Ba) and could contribute to the degassing mass balance of some volatile trace elements, provided they are mobile in F-rich fluids. It thus appears that both primary magmatic degassing and secondary tephra dissolution processes govern the chemistry of eruptive plumes released during explosive eruptions.     

Composition,structure, origin,and evolution of off-axis linear volcanic structures of the Brazil Basin,South Atlantic

The paper considers the conditions and mechanisms of the formation of linear volcanic structures in the Brazil Basin, South Atlantic. Among these objects, those related to the ascent of deep mantle plumes predominate. It is shown that the ascent of melts from plume sources leads to the formation of (a) hot spot tracks in the form of linear volcanic ridges and (b) active hot lines in the form of submarine mountain chains with trends differing from those of hot spot tracks and with a more variable character of the age distribution of volcanic rocks. Fault tectonics affects the character of plume activity. In addition, plume material from a hot spot area is dragged by a moving plate as a flow or a sublithospheric lens, which leads to the long-term existence of particular independent segments of linear structures and sometimes to late volcanism reactivation within their limits. Decompression melting of the asthenospheric mantle in zones where thin lithosphere undergoes tension causes the formation of passive hot lines. The main mantle source for the considered volcanic rocks was a mixture of DMM and HIMU mantle components, with the latter abruptly dominating. In marginal oceanic regions, the EM1 component is also present (the EM2 component is found more rarely) within fragments of tectonically delaminated continental mantle that was trapped by the oceanic mantle during the breakup of Gondwana.     

Environmental impact of the acid fumarolic plume of a passively degassing volcano (Vulcano Island,Italy)

This paper investigates the role played by the fumarolic plume of a passive degassing volcano in the genesis of rock coatings (RC) and in the introduction and re-distribution of metals and trace elements in the surficial environment. At La Fossa active volcano (Vulcano Island) and in the surrounding environment RC develop owing to exposure of the ground surface to the volcanic acid plume produced by the passive degassing of La Fossa. Significant positive anomalies of a wide variety of metals and trace elements (including Bi, Ag, Se, Te, Sb, Pb, As, Cu, Tl and Cd) were observed either in distal and proximal RC. Most of these anomalies are interpreted to be the result of the transport and subsequent deposition of trace elements, likely to form volatile compounds, in the fumarolic plume. Two main processes seem to control the geochemistry of RC: one is represented by the leaching and subsequent deposition of elements from the proximal toward the distal RC; the other is the direct input of trace elements carried by the emitted volcanic aerosol. The fact that most of the trace elements (particularly Pb, As, Tl, Bi, Te, Se, Cd) enriched in the RC of Vulcano are highly toxic and potentially dangerous to health in high concentration, indicates that the atmospheric metal injection by the quiescently degassing La Fossa volcano together with the subsequent deposition and remobilization by means of surficial waters may represent an environmental hazard that should be taken into account in evaluating the potential impact of volcanic air pollution on human health.     

松辽盆地土壤溴的地球化学特征及其对油气的指示

Br和I是卤族元素的重要成员,I用于油气勘查取得了较好的找矿效果,但是,目前还未见到国外有关Br元素勘查油气的报道。应用松辽盆地中部8.15×104km2的多目标地球化学勘查数据,在研究土壤Br元素近地表影响因素的基础上,试验了表层土壤Br和深层土壤Br的区域地球化学异常对油气的指示意义。在松辽盆地中部发现了表层土壤Br的地球化学巨省和深层土壤Br的地球化学巨环,它们与油气富集区带、大中型油气田和火山岩油气藏相联系。土壤Br元素的表生地球化学作用和油气微渗漏是表层巨省和深层巨环形成的主要机制,因而,土壤Br元素也是战略性油气地球化学填图的一个新的辅助指标。     

Tectonotype of volcanic passive margins in the Norwegian-Greenland region

A tectonotype of volcanic passive margins exemplified in the conjugate Norwegian and East Greenland margins is considered, with discussion of the Paleogene igneous complexes and the regional rift structure before continental breakup. Fragments of asymmetrical rift have been retained on both sides of the ocean. Large Cretaceous pre-rift sedimentation basins marking the initial stage of the ocean opening are included into the passive margin as well. The continental breakup was accompanied by intense basaltic magmatism over a short time span. This magmatic episode was distinguished by (1) the formation of widespread plateau-basalt complexes on continents and in near-shore areas of the ocean; (2) the development of thick lava series that are recorded in seaward dipping reflector wedges; (3) thick high-velocity lower crust, resulting from magmatic underplating; (4) asymmetrical accretion of the crust and structure formation. The discussion is based on published seismic data and reference sections selected for each margin with consideration of the composition and thickness of the igneous rocks, their lateral variations, source composition, and eruption and crust formation conditions. The characteristic feature of both sections is the two-member structure of volcanic complexes with substantial geochemical differences between the rocks from the lower and upper parts of the section, which correspond to the pre-breakup and breakup phases. At the initial phase, small magma volumes were melted out from the lithosphere. The geochemical signatures of the upper parts of the sections testify to the melting of the asthenospheric mantle. Their spatiotemporal variations reflect the ascent and melting of the deep plume, which was active during and after continental breakup. In the Greenland area, near the central part of the plume, a N-MORB-type mantle magma source gave way to a depleted Iceland-type mantle, while apart from the central part of the plume, its effect is expressed only in the enormous volume of mantle-derived melt without migration of its source. A variety of evidence is provided for the plume’s activity: the great thickness of the volcanic complexes and the relatively stable composition of the melt; the elevated temperature in the mantle; the specific geochemistry of the breakup-related lavas and their lateral zoning; conclusions on the necessity of dynamic support of volcanic eruptions; and recent results of seismographic tomography. The continental breakup inherited a system of older sedimentary basins in the zone of prolonged extension of the lithosphere in the North Atlantic. The continuous dynamic support of extension was most likely provided by long-term ascent of the Iceland plume. The comparison of the considered tectonotype with other volcanic and non-volcanic margins opens the way to further elucidation of the geodynamic processes responsible for the ocean opening.     

Tephra Fallout Models: The Effect of Different Source Shapes on Isomass Maps

Numerous tephra dispersion and sedimentation models rely on some abstraction of the volcanic plume to simplify forecasts of tephra accumulation as a function of the distance from the volcano. Here we present solutions to the commonly used advection–dispersion equation using a variety of source shapes: a point, horizontal and vertical lines, and a circular disk. These may be related to some volcanic plume structure, such as a strong plume (vertical line), umbrella cloud (circular disk), or co-ignimbrite plume (horizontal line), or can be used to build a more complex plume structure such as a series of circular disks to represent a buoyant weak plume. Basing parameters upon eruption data, we find that depositions for the horizontal source shapes are very similar but differ from the vertical line source deposition. We also compare the deposition from a series of stacked circular disk sources of increasing radius above the volcanic vent with that from a vertical line source.     

中国北方大陆下的地幔热柱与岩石圈运动

本文首次提出中国北方大陆下存在一个地幔热柱的论证,并提出亚热柱(sub—plume)的新概念。热柱的中心与边缘部分的隙间熔浆分别为苦橄质玄武岩与碱性玄武岩。在渐新世到中新世约18.4 Ma内,北方大陆以3.26cm/a的速率向东南飘移了约600km,使日本海、渤海—华北平原等脱离热柱。导致晚第三纪日本海扩张的停止,渤海—华北平原等早第三纪火山喷发的突然中止。火山喷发期间,在热柱头部若干个亚热柱的形成,好似若干个“铆钉”穿入岩石圈,有效地阻止了岩石圈的飘移(这时的飘移速率只有0.05cm/a),我们把火山喷发称为固定岩石圈的“铆钉效应”。     

Field study and laboratory experiments of bubble plumes in shallow seas as analogues of sub-seabed CO2 leakages

To understand the effects of increased levels of CO₂ on the marine realm, it is possible to study areas where, for natural reasons, there are emissions of CO₂ from the seabed. One of these areas is located east of Panarea Island (Aeolian Islands – Southern Tyrrhenian Sea – Italy). Here, the volcanic activity that characterizes the Aeolian archipelago causes a continuous release of CO₂ (up to 98% of the total gas) from several vents on the seafloor in shallow water. This area was studied by means of surface techniques and direct SCUBA diving surveys; the data presented refers to a field campaign performed in 2008. To collect the necessary data, some dedicated sampling and measuring techniques were developed for use in an underwater environment. The chemistry of the fluids and their influence on the water body was determined via logs and transects in the field and by gas-chromatographic and liquid-chromatographic laboratory analysis. The flux from some of the main gas vents was also measured directly underwater. Furthermore, some laboratory experiments in a two-layer stratified fluid were conducted to understand the main features of the physical interaction of a gas plume with the surrounding environment. Both field and laboratory experiments show that there is a development of a pseudo-convective cell around the rising plume with the formation of vortices that act as a physical barrier thus reducing the interaction between the plume and the surrounding water.     

The environmental influence of a volcanic plume,a new technique of study,Mount Etna,sicily

Detailed study of the chemistry of volcanic plumes has previously been hindered by the difficulties of sampling, particularly if data on trace elements are required. In an attempt to overcome this problem, and to learn more about the regional effects of the plume of Mt. Etna, it was decided to investigate whether lichens, which are used as indicators of aerial pollution, would be suitable for this type of study. Samples collected from the slopes of Etna were assayed, mainly for heavy metals. The results show that this technique has great potential, that lichens can be used to determine semiquantitatively the minor and trace element composition of the plume, and can detect the influence of the plume on the chemistry of local rainfall.     

Hydrogen isotopes in volcanic plumes: Tracers for remote temperature sensing of fumaroles

In high-temperature volcanic fumaroles (>400 °C), the isotopic composition of molecular hydrogen (H₂) reaches equilibrium with that of the fumarolic H₂O. In this study, we used this hydrogen isotope exchange equilibrium of fumarolic H₂ as a tracer for the remote temperature at volcanic fumaroles. In this remote sensing, we deduced the hydrogen isotopic composition (δD value) of fumarolic H₂ from those in the volcanic plume. To ascertain that we can estimate the δD value of fumarolic H₂ from those in a volcanic plume, we estimated the values in three fumaroles with outlet temperatures of 630 °C (Tarumae), 203 °C (Kuju), and 107 °C (E-san). For this we measured the concentration and δD value of H₂ in each volcanic plume, along with those determined directly at each fumarole. The average and maximum mixing ratios of fumarolic H₂ within a plume’s total H₂ were 97% and 99% (at Tarumae), 89% and 96% (at Kuju), and 97% and 99% (at E-san). We found a linear relationship between the depletion in the δD values of H₂, with the reciprocal of H₂ concentration. Furthermore, the estimated end-member δD value for each H₂-enriched component (−260 ± 30‰ vs. VSMOW in Tarumae, −509 ± 23‰ in Kuju, and −437 ± 14‰ in E-san) coincided well with those observed at each fumarole (−247.0 ± 0.6‰ in Tarumae, −527.7 ± 10.1‰ in Kuju, and −432.1 ± 2.5‰ in E-san). Moreover, the calculated isotopic temperatures at the fumaroles agreed to within 20 °C with the observed outlet temperature at Tarumae and Kuju. We deduced that the δD value of the fumarolic H₂ was quenched within the volcanic plume. This enabled us to remotely estimate these in the fumarole, and thus the outlet temperature of fumaroles, at least for those having the outlet temperatures more than 400 °C. By applying this methodology to the volcanic plume emitted from the Crater 1 of Mt. Naka-dake (the volcano Aso) where direct measurement on fumaroles was impractical, we estimated that the δD value of the fumarolic H₂ to be −172 ± 16‰ and the outlet temperature to be 868 ± 97 °C. The remote temperature sensing using hydrogen isotopes developed in this study is widely applicable to many volcanic systems.     

Evaluation of the environmental impact of volcanic emissions from the chemistry of rainwater: Mount Etna area (Sicily)

The S, halogen and NO₃ contents of rainwater samples from the Etnean area were studied in order to define the environmental impact of plume emissions on the local environment. Samples, collected on a network of 11 bulk rain gauges, show significant variability in anion content, which can be ascribed to different meteorological and environmental conditions at each sampling site and to a variable distance from the different source areas. Data analysis suggests that S, F, Cl and Br are mainly magma-derived, whereas NO₃ mainly originates from anthropogenic sources. Samples collected from sites close to craters display considerable temporal variability, with increased anion concentrations being recorded during periods of intense plume degassing. Variations in precipitation also induce significant modifications in the chemistry of the meteoric-derived Etnean groundwaters.     

对流层活性卤素化学:充满机遇和挑战的研究领域

活性卤素物种(RHS)参与大气对流层中许多化学过程,影响许多重要物种的源和汇,在大气对流层化学中起着十分重要的作用,因此对流层活性卤素化学成为近年来国际大气化学研究的重要前沿研究领域。RHS在对流层的外场观测方法主要包括化学放大、大气压化学电离质谱（APCIMS）、长程差分吸收光谱（DOAS）、雾室和湿法化学分析法、光解法、碳同位素的比率法等。各种观测方法表明大气边界层中存在着不同种类的RHS,特别在海洋边界层、极地边界层和盐湖地区。RHS的浓度有较大的变化范围（10-12~10-10）。RHS可引起一些VOCs的氧化,影响HOx和NOx的反应,减少对流层O3,并对硫的氧化和汞化学有较大的影响。对流层RHS的源主要为有机卤素化合物的排放和海盐气溶胶的释放。在讨论RHS在对流层的循环转化的基础上,归纳总结出一个示意图;提出了现有的主要科学问题,进而展望了今后的研究前景。     

Early detection of volcanic hazard by lidar measurement of carbon dioxide

Volcanic gases give information on magmatic processes. In particular, anomalous releases of carbon dioxide precede volcanic eruptions. Up to now, this gas has been measured in volcanic plumes with conventional measurements that imply the severe risks of local sampling and can last many hours. For these reasons and for the great advantages of laser sensing, the thorough development of volcanic lidars has been undertaken at ENEA (Italian National Agency for New Technologies, Energy and Sustainable Economic Development). In fact, lidar profiling allows one to scan remotely volcanic plumes in a fast and continuous way, and with high spatial and temporal resolution. A differential absorption lidar instrument will be presented in this paper: BILLI (BrIdge voLcanic LIdar). It is based on injection-seeded Nd:YAG laser, double-grating dye laser, difference frequency mixing and optical parametric amplifier. BILLI is funded by the ERC (European Research Council) project BRIDGE (BRIDging the gap between Gas Emissions and geophysical observations at active volcanos). It scanned the gas emitted by Pozzuoli Solfatara (Naples, Italy) and Stromboli Volcano (Sicily, Italy) during field campaigns carried out from October 13 to 17, 2014, and from June 24 to 29, 2015, respectively. Carbon dioxide concentration maps were retrieved remotely in few minutes in the crater areas. To our knowledge, it is the first time that carbon dioxide in a volcanic plume is retrieved by lidar. This result represents the first direct measurement of this kind ever performed on active volcanos and shows the high potential of laser remote sensing in early detection of volcanic hazard.     

滇东南建水地区高镁火山岩包体的成因和构造背景

在滇东南建水地区发现产于峨眉山玄武岩中的高镁火山岩包体,这对于地幔柱的形成演化具有重要研究意义.对这些包体进行了锆石U-Pb年代学、地球化学和岩矿分析.高镁火山岩包体具斑状结构,致密块状构造,斑晶主要为贵橄榄石和透辉石.13颗锆石U-Pb LA-ICP-MS加权平均年龄为259±2Ma(MSWD=1.9),显示与寄主岩石同期形成.包体岩石具有高镁(Mg~#=68～75)、低硅(SiO_2=45.11%～45.93%)特征,轻稀土元素(LREE)、高场强元素(HFSE)富集而重稀土元素(HREE)亏损,属于亚碱性、拉斑玄武岩系列,具有板内玄武岩(IPB)特征.火山岩包体的原始岩浆起源于石榴子石二辉橄榄岩低程度部分熔融的产物,岩浆演化过程中发生了橄榄石和单斜辉石的分离结晶作用,在侵位上升过程中未受明显的地壳混染作用.该高镁火山岩的存在,显示地幔柱除了垂直上升运动外,在地球深部不同的边界还有多次侧向扩展移动,表明滇东南晚二叠世存在峨眉山地幔柱的一个分支-地幔枝活动.     

中国东北地区中生代火山岩的大地构造意义

中国东北地区中生代火山岩可划分为西部大兴安岭环状火山岩带、南部火山岩带和东部火山岩带,它们是古亚洲洋构造域向太平洋构造域转换时期不同构造环境的产物。西部大兴安岭环状火山岩带的形成与古亚洲洋闭合过程中壳幔相互作用引起的深部热地幔柱的上升有关,南部火山岩带与构造域转换时期走滑拉伸构造有关,而东部火山岩带则是太平洋板块斜向俯冲作用的产物。     

Determination of Bromine and Iodine in U.S.G.S. Standard Marine Mud (MAG-1)

The concentrations of bromine and iodine in USGS reference material MAG-1 were determined by standard addition with secondary-source x-ray fluorescence spectrometric detection. Three determinations of bromine in the same sample yielded 311, 309 and 346 μg Br/g solid. The iodine content was found to be 380 μg I/g solid. The determination of bromine in a second bottle of MAG-1 (266 ± 9 μg Br/g) indicated that a large variation in halogen concentration may exist between samples of this reference material.     

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.     

藏南曲卓木地区酸性火山岩地球化学、Hf-Sr-Nd同位素特征及其成因

目前关于白垩纪酸性岩石的相关研究报道极少.近年来在曲卓木地区发现了较为广泛的酸性（英安岩）-基性（辉绿岩-玄武岩）火山岩浆活动,双峰式火山岩浆活动特征明显.对其进行了年代学、地球化学及Hf-Sr-Nd同位素研究.结果表明,英安岩成岩年龄为142.0±2.5 Ma,具有高的LREE及Nb、Zr、Hf、Y等高场强元素含量以及Ga/Al比值,显示A型花岗岩特征.锆石的ε_Hf（t）值为-13.1~-2.4,平均值为-7.1.岩石具有高的初始Sr同位素值（（87Sr/86Sr）_i值为0.722 024~0.722 698）以及低的初始Nd同位素值（ε_Nd（t）为-12.2~-11.8）.综合研究表明,曲卓木地区酸性火山岩是伸展背景下大陆地壳深熔作用的产物,其与区域上桑秀组酸性火山岩、Laguila酸性侵入岩、桑日则地区流纹岩具有相似的地球化学特征与相当的成岩年龄,可能同属于Comei-Bunbury大火成岩省的一部分,均是Kerguelen地幔柱早期岩浆活动产物,而Kerguelen地幔柱活动可能提前至140 Ma左右.      

Chemical monitoring of volcanic gas using remote FT-IR spectroscopy at several active volcanoes in Japan

Chemical compositions of volcanic gases of several Japanese active volcanoes have been monitored from distant safe places since the beginning of the 1990s using an FT-IR spectral radiometer. For absorption measurements, an infrared light source behind volcanic gas emissions is necessary in a volcanic environment. In the early observations, infrared radiation from hot lava domes (Unzen volcano) and hot ground heated by high-temperature fumaroles (Usu, Aso, and Satsuma-Iwojima volcanoes) were used as infrared light sources. However, these sources were not available in many cases. This remote FT-IR method became more commonly applied to chemical monitoring of volcanic gases emitted from the summit or slopes of active volcanoes using scattered solar infrared light as infrared light sources (Sakurajima, Miyakejima, and Asama volcanoes). To date, eight species have been measured using this method: SO₂, HCl, HF, CO, CO₂, COS, SiF₄, and H₂O. The observations indicate that volcanic gases for each volcano have different chemical composition on a SO₂–HCl–HF ternary diagram in spite of similar tectonic settings, suggesting that vapor/melt volume ratios during volcanic gas formation differ among volcanoes. During more than 15 years of monitoring, chemical changes in volcanic gases attributable to ascent of magma were observed only at Asama, where HCl/SO₂ and HF/HCl ratios in the eruptive period were higher than those in non-eruptive period because of scrubbing of more soluble components in surface hydrothermal systems in the non-eruptive stage or solubility-controlled fractionation processes. Results show that these parameters are the most prospective ones among the various parameters measured using the remote FT-IR method to monitor volcanic activities.