铊同位素及环境示踪研究进展

近年来随着多道接收电感耦合等离子体质谱仪(MC-ICPMS)的广泛应用,铊(Tl)同位素成为当前非传统同位素地球化学研究热点之一。本文综述了Tl同位素的最新研究进展。Tl是自然界迄今为止发现的具有同位素自然分馏效应的最重的元素之一。自然界中Tl同位素分馏值ε205Tl(ε205Tl指样品与标准物质NIST SRM 997 Tl的205Tl/203Tl值的万分偏差)的变化为-6.8~+4.8,陨石中ε205Tl值为-18.8~+29.7。Tl同位素可用于示踪低温过程中的物质迁移、海洋沉积物沉积过程等,也可用于指示古气候的变化,以及佐证特定时期有机碳输出量。因此,Tl同位素可为深入了解局域海洋沉积环境的氧化还原条件、碳循环和海洋化学演化等提供新信息,将在地学与环境科学研究中得到广泛应用。     

本期文章导读

正非传统稳定同位素地球化学的建立与发展是本世纪地球化学领域的重要进展之一。镉(Cd)同位素分馏主要发生在蒸发/冷凝过程、无机吸附/沉淀过程及生物吸收利用过程。这些Cd同位素分馏效应被成功应用于构建海洋生物地球化学Cd循环体系、反演古海洋环境及初级生产力变化,硫化物矿床成矿流体演化、成矿物质来源示踪及不同成因矿床类型判别研究,环境体系Cd污染源的源区判别、农田面源Cd来源及其运移、循环及储存机制研究。在海洋科学、地球科学、环境科学及农业科学研究上展现出巨大的应用潜力。该文提出下一步应深入开展高精度Cd同位素分析方法研究,探讨Cd同位素分馏机制和分馏模型,尤其是应深入研究微生物作用下Cd同位素分馏效应,建立Cd同位素生物分馏地球化学示踪体系,推动非传统稳定同位素地球化学创新发展。     

镉稳定同位素研究进展

Cd具有挥发性和亲硫性,在海洋环境中Cd为微量营养元素,而在生态环境及农业土壤环境中Cd为有毒元素。因此,镉同位素被应用于海洋科学、地球科学、环境科学及农业科学研究,并展现出巨大的应用潜力。本文总结了近年来富含有机质的环境样品、植物样品和生物样品的消解方法,以及Cd分离纯化及双稀释剂校正方法的研究进展。采用微波、高压灰化和高氯酸消解等样品前处理方法均可消除有机质对镉同位素测定的影响;基于AG MP-1(M)树脂-盐酸淋洗体系可有效分离基体及干扰元素,不会导致镉同位素分馏;^(111 )Cd-^(113 )Cd同位素双稀释剂校正体系的测试精度高,可达0.1εCd/amu。同时,本文阐述了镉同位素在海洋科学、地球科学、环境科学及农业科学领域研究的最新进展和认识。镉同位素已成功应用于构建海洋生物地球化学Cd循环体系、反演古海洋环境及初级生产力变化,硫化物矿床成矿流体演化、成矿物质来源示踪及不同成因矿床类型判别研究,环境体系Cd污染源的源区判别、农田面源Cd来源及其运移、循环及储存机制研究。本文提出需要进一步开展镉同位素分馏机制及分馏模型的研究,构建Cd稳定同位素地球化学体系。     

植物中Cd同位素分馏特征研究——以Cd超富集植物龙葵及耐性植物蓖麻为例

<正>Cd是一种剧毒重金属元素,容易通过食物链的富集作用进入人体危及人类健康,Cd污染一直是科学界重视的研究课题之一,查明Cd污染源并从源头上加以控制,对实施污染治理改变环境现状具有十分重要的意义。近年来,多接收电感耦合等离子体质谱仪(MC-ICPMS)的发展拓宽了Cd同位素的应用范围,Cd同位素已成功应用到陨石样品、海洋样品和岩石样品,研究行星演化、海洋体系的物质与循环,也逐渐的用于现代环境科学领域示踪Cd元素的污染来源,而对于植物中Cd同位素分馏特征研究报道较少,高等植物生命活动过程中Cd同位素的分馏、分馏大小及主要影响因素均尚不清楚。本研究通过对不同淋洗     

氧化还原敏感元素(Se,Cr,Mo)稳定同位素

由于同位素分析方法的改进及表面热离子质谱(TIMS)和多接收电感耦合等离子体质谱(MC-ICP-MS)的应用,近年来氧化还原敏感元素(Se、Cr、Mo)同位素地球化学得以快速发展,成为国际地学领域的一个前沿。Se同位素在自然界中的变化最大,δ82/76SeNIST为-12.77‰～3.04‰;Cr和Mo同位素变化较小,δ53/52CrNIST值为-0.07‰～0.37‰,δ97/95MoJMC值为-0.27‰～2.65‰。自然界中各种无机过程(氧化还原)和生物有机过程均能使Se、Cr、Mo产生同位素分馏。因此,这些氧化还原敏感元素同位素可以示踪环境污染源、矿床流体来源;解释古海洋与现代海洋中元素的自身循环,从而示踪古氧化还原环境的演化;解释地外撞击事件及宇宙行星演化;甚至在生物学等领域研究中取得了显著成效。虽然还存在一些问题但它们将可能成为地球科学中有巨大应用前景的一种新兴的地球化学工具。     

榴辉岩部分熔融过程中的同位素分馏

本文对榴辉岩部分熔融过程中不同同位素体系是否存在分馏这一当前研究热点进行了综述。榴辉岩作为研究洋陆俯冲、超高压变质以及壳幔相互作用的主要岩石类型,其部分熔融与地壳增生、板片折返过程以及俯冲隧道中元素的迁移分配等具有紧密的联系。作为典型的高压-超高压变质岩石,榴辉岩可通过俯冲带将壳源信息携带至地幔深部,影响地幔的化学组成,并可在大洋玄武岩中得以表现。近些年,随着仪器分析技术的发展,实验研究和理论计算均表明榴辉岩部分熔融过程中稳定同位素可以产生显著的分馏。作为常见的放射性成因子体同位素和传统稳定同位素Sr-Nd-Hf-O被广泛应用于源区示踪、岩浆混合以及结晶分异等过程。但目前有研究指出,在非平衡熔融过程中,熔体和源区的Sr-Nd-Hf-O同位素可发生解耦,导致二者的同位素组成不均一。另外,通过研究榴辉岩及其熔融产物的金属稳定同位素特征,发现榴辉岩部分熔融过程中,由于石榴石效应,会造成Ca、Mg、Fe、Li等金属稳定同位素的分馏。因此,当利用稳定同位素示踪榴辉岩熔体的源区时,需要考虑其分馏的影响。     

汞的稳定同位素分馏机理

汞是唯一能够以气态单质形式进行长距离传输的有毒重金属元素,其环境行为和健康危害受到广泛关注.近十多年来发展起来的汞稳定同位素技术为研究环境中汞的来源、迁移转化过程以及相应的生态环境效应提供了新的视野.汞同位素是自然界中唯一表现出多种显著非质量分馏(MIF)的独特金属同位素体系,对汞同位素的研究一直偏重应用,而对其分馏机理的认识十分有限.本文从汞稳定同位素分馏理论、分馏实验研究和实际环境过程的汞同位素分馏三方面系统阐述了近十多年来关于汞同位素分馏机理的研究成果、最新进展和未来发展方向.尽管目前的研究普遍认为无机汞的光化学氧化还原和甲基汞的光化学降解是环境中汞同位素MIF的主要产生机制,然而MIF程度和方向的影响因素还不完全清楚,其量化理论还未完全建立,实际环境过程中的分馏机理研究还相对缺乏.未来需要结合理论和实验研究进一步明确大气、陆地、海洋、极地、古环境等实际环境体系中的汞同位素分馏机理,进而拓展汞同位素的应用.     

地球科学中铁同位素研究进展

21世纪初,铁同位素的高精度分析因多道等离子体质谱仪的引入成为可能。铁在自然界中具有高丰度、多价态和生物可利用性,其同位素地球化学受到广泛关注,并取得巨大的进展。本文综述了铁同位素研究的进展和在地球科学中的应用。这些进展包括：(1)查明了各类陨石的铁同位素组成,并制约了太阳系及早期行星演化过程;(2)调查了地球主要储库的铁同位素组成;(3)积累了大量高、低温常见体系中两相间的铁同位素分馏系数;(4)初步探明了岩浆过程(如部分熔融、地幔交代和岩浆分异等)中的铁同位素分馏行为;(5)初步查明铁同位素在主要低温过程(如风化、早期成岩作用等)中的分馏行为;(6)实例性研究揭示了沉积岩样品铁同位素在示踪古海洋大气氧逸度变化和早期生命演化方面的潜力。随着人们对铁同位素分馏机制理解的加深,各体系中分馏系数的积累,铁同位素将在地球科学的各个方面得到更广泛的应用。     

高温下非传统稳定同位素分馏

过去十几年来,非传统稳定同位素地球化学在高温地质过程的研究中取得了的重大进展。多接收诱导耦合等离子质谱(MC-ICP-MS)的应用引发了稳定同位素分析方法的重大突破,使得精确测定重元素的同位素比值成为可能。本文总结了以Li、Fe和Mg同位素为代表的非传统稳定同位素在岩石地球化学研究中的应用。Li同位素目前被广泛地用于地幔地球化学、俯冲带物质再循环和变质作用的研究中,可以用来示踪岩浆的源区性质和扩散等动力学过程。不同价态的Fe在矿物熔体相之间的分配可以产生Fe同位素分馏,可以发生在地幔交代、部分熔融、分离结晶等过程中。岩浆岩的Mg同位素则大致反映其源区的特征,地幔的Mg同位素组成比较均一,这为研究低温地球化学过程中Mg同位素的分馏提供一个均一的背景。此外,Cl,Si,Cu,Ca,U等等同位素体系也具有广阔的应用前景。对同位素分馏机制的实验研究和理论模拟为理解非传统稳定同位素数据提供了必要的指导。实验表明,高温下具有不同的迁移速度的轻、重同位素可以产生显著的动力学同位素分馏,这一分馏可以在化学扩散、蒸发和凝华等过程中发生;同位素在矿物和熔体以及流体相中化学环境的差异使得不同相之间可以发生平衡分馏。而最近的硅酸盐岩浆的热扩散和热迁移实验则揭示了一种"新"的岩浆分异和同位素分馏机制。沿着温度梯度,硅酸盐岩浆可以发生显著的元素和同位素分异,湿的安山岩可以通过这种方式演变成花岗质成分,因此这个过程可能对陆壳的产生和演化有重大影响。如果温度梯度在岩浆作用中能长期存在,热扩散就可以产生稳定同位素的分馏,这一机制有别于传统的平衡和动力学同位素分馏。 而多个稳定同位素体系的正相关关系是示踪热迁移过程的最有力证据。在热扩散过程中,流体承载的物质的浓度和它的索瑞系数有关。但是这个系数对体系的很多参数非常敏感,变化极大,因此对热扩散效应的研究产生极大的困难。对热扩散实验的镁、钙和铁同位素测量表明,同位素比值的变化与体系的化学组成以及总温度无关,只和温度变化的幅度有关,这意味着即使元素的索瑞系数变化多端,某一元素的同位素之间的索瑞系数的差别总为常数。这一发现有助于简化对热扩散和索瑞系数这一基础物理问题的研究 。     

基于金属稳定同位素的矿冶影响区土壤重金属污染源解析研究进展

矿冶影响区重金属的迁移和富集造成了严重的土壤重金属污染问题。深入了解矿冶影响区土壤中重金属的来源和迁移途径是开展土壤重金属污染高效治理的科学基础。近年来飞速发展的金属稳定同位素在识别土壤重金属污染来源和明确重金属迁移过程等方面有较大的应用优势。对金属稳定同位素分析技术、示踪原理及溯源模型进行系统分析,综述了矿产开采及冶炼过程（高温冶炼、电化学工艺和尾矿风化）导致的金属稳定同位素分馏研究进展,并总结了金属稳定同位素在矿冶影响区土壤重金属污染源解析的代表性应用成果。V同位素体系处于初期研究阶段,土壤重金属源解析应用研究相对缺乏;Zn、Cd和Hg同位素在识别高温冶炼过程相关的重金属污染源时有较大优势;Cu、Tl和Ni同位素可直接指示土壤中矿石的输入。但是,目前还存在部分金属稳定同位素分析难度大、溯源模型应用限制多、金属同位素易发生分馏导致源不确定等问题。在未来的工作中,需进一步探索和优化金属同位素分析方法,建立更多金属稳定同位素指纹图谱,开发适用性更强、结果更精确的溯源模型,明确复杂界面过程和反应中的金属稳定同位素分馏特征及机理,加强金属稳定同位素在追溯土壤重金属污染形成的时间尺度等方面的实...     

无机地球化学参数与有效烃源岩发育环境的相关研究

探索海相有效烃源岩判识指标仍是我国油气勘探中尚待解决的重要科研任务之一。古生产力及氧化还原条件是研究全球变化和海洋环境的重要内容,也是重塑有效烃源岩发育环境的主要参数。Si、Ba是古生产力的替代指标,Cd对古营养盐的反演具良好前景。过渡金属及其相关比值是缺氧环境的有效判识指标,可用其推断有机质保存条件。δ13Ccarb正偏移指示有机质埋藏量增加,是底部水体缺氧的响应。过渡金属同位素（δ65Cu、δ66Zn、δ97Mo）受生物活动及氧化还原条件的影响发生较大分馏,示踪环境变化具灵敏、高效性。将这些无机参数对古环境的示踪意义引入油气地质研究,从环境角度分析某一套地层能否发育有效烃源岩,进而探讨高演化海相有效烃源岩的判识,就更具特殊意义。     

Geochemistry of trace element in carbonaceous sediments from recent seas and oceans

Published and original data on the contents of 50 elements in carbonaceous sediments from seas (Black, Baltic, and Caspian) and fertile oceanic shelves (shelves of Namibia, Peru, Chile, and California) are generalized. The comparison of these results with the average composition of ancient carbonaceous shales reveals both similarities and differences in the distribution of indicator trace elements (Re, Hg, Se, Ag, Cd, Tl, U, Mo, As, Ni, and Zn). Correlation coefficients were analyzed to determine the characteristic element associations. It is established that oceanic carbonaceous sediments are closer in composition to carbonaceous shales than their marine analogues, which is related to the differences in sedimentation conditions, including hydrological, hydrochemical, and biogeochemical factors. The role of anoxic environment in the accumulation of chalcophile elements in sediments is estimated. The comparison of the contents of some mobile trace elements in oceanic water and carbonaceous sediments of modern oceans demonstrates that the water composition affects the composition of carbonaceous sediments and can be used for deciphering the composition of ancient ocean water.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

GEOTRACES - An international study of the global marine biogeochemical cycles of trace elements and their isotopes

Trace elements serve important roles as regulators of ocean processes including marine ecosystem dynamics and carbon cycling. The role of iron, for instance, is well known as a limiting micronutrient in the surface ocean. Several other trace elements also play crucial roles in ecosystem function and their supply therefore controls the structure, and possibly the productivity, of marine ecosystems. Understanding the biogeochemical cycling of these micronutrients requires knowledge of their diverse sources and sinks, as well as their transport and chemical form in the ocean.Much of what is known about past ocean conditions, and therefore about the processes driving global climate change, is derived from trace-element and isotope patterns recorded in marine deposits. Reading the geochemical information archived in marine sediments informs us about past changes in fundamental ocean conditions such as temperature, salinity, pH, carbon chemistry, ocean circulation and biological productivity. These records provide our principal source of information about the ocean's role in past climate change. Understanding this role offers unique insights into the future consequences of global change.The cycle of many trace elements and isotopes has been significantly impacted by human activity. Some of these are harmful to the natural and human environment due to their toxicity and/or radioactivity. Understanding the processes that control the transport and fate of these contaminants is an important aspect of protecting the ocean environment. Such understanding requires accurate knowledge of the natural biogeochemical cycling of these elements so that changes due to human activity can be put in context.Despite the recognised importance of understanding the geochemical cycles of trace elements and isotopes, limited knowledge of their sources and sinks in the ocean and the rates and mechanisms governing their internal cycling, constrains their application to illuminating the problems outlined above. Marine geochemists are poised to make significant progress in trace-element biogeochemistry. Advances in clean sampling protocols and analytical techniques provide unprecedented capability for high-density sampling and measurement of a wide range of trace elements and isotopes which can be combined with new modelling strategies that have evolved from the World Ocean Circulation Experiment (WOCE) and Joint Global Ocean Flux Study (JGOFS) programmes. A major new international research programme, GEOTRACES, has now been developed as a result of community input to study the global marine biogeochemical cycles of trace elements and their isotopes. Here, we describe this programme and its rationale.     

古海洋生产力指标研究进展

寻求反映古海洋生产力变化的指标是古海洋学研究的重要内容。生物沉积物、营养元素、微量元素和同位素、古生物资料等与古海洋生产力具有一定的关系,常用于古海洋生产力的重建工作:(1)生物沉积物主要包括有机碳、生物碳酸盐和生物硅质沉积等,其埋藏速率在很大程度上受到古海洋生产力的控制,常常用作古海洋生产力的替代性指标;(2)在地质时间尺度上,古海洋生产力主要受到大洋中营养元素可利用程度的控制,因此营养元素的相关记录可以提供古海洋生产力状况的重要信息;(3)海洋中某些微量元素的地球化学行为或者与有机质的改造有关,或者受到氧化还原条件变化的控制,或者受到某种浮游生物的生长的影响,从而能够直接或者间接地指示古海洋生产力的变化;(4)海相碳酸盐和有机质的碳同位素记录,海相有机物的氮同位素比值也用以再造古生产率等古海洋学参数;(5)可以利用对微体化石丰度值及其组合反映古生产力的变化。     

Trace Elements and Rare Earth Elements of Sulfide Minerals in the Tianqiao Pb-Zn Ore Deposit, Guizhou Province, China

Trace elements and rare earth elements (REE) of the sulfide minerals were determined by inductively-coupled plasma mass spectrometry. The results indicate that V, Cu, Sn, Ga, Cd, In, and Se are concentrated in sphalerite, Sb, As, Ge, and Tl are concentrated in galena, and almost all trace elements in pyrite are low. The Ga and Cd contents in the light-yellow sphalerites are higher than that in the brown and the black sphalerites. The contents of Ge, Tl, In, and Se in brown sphalerites are higher than that in light-yellow sphalerites and black sphalerites. It shows that REE concentrations are higher in pyrite than in sphalerite, and galena. In sphalerites, the REE concentration decreases from light-yellow sphalerites, brown sphalerites, to black sphalerites. The ratios of Ga/In are more than 10, and Co/Ni are less than 1 in the studied sphalerites and pyrites, respectively, indicating that the genesis of the Tianqiao Pb–Zn ore deposit might belong to sedimentary-reformed genesis associated with hydrothermal genesis. The relationship between LnGa and LnIn in sphalerite, and between LnBi and LnSb in galena, indicates that the Tianqiao Pb–Zn ore deposit might belong to sedimentary-reformed genesis. Based on the chondrite-normalized REE patterns, δEu is a negative anomaly (0.13–0.88), and δCe does not show obvious anomaly (0.88–1.31); all the samples have low total REE concentrations (<3 ppm) and a wide range of light rare earth element/high rare earth element ratios (1.12–12.35). These results indicate that the ore-forming fluids occur under a reducing environment. Comparison REE compositions and parameters of sphalerites, galenas, pyrites, ores, altered dolostone rocks, strata carbonates, and the pyrite from Lower Carboniferous Datang Formation showed that the ore-forming fluids might come from polycomponent systems, that is, different chronostratigraphic units could make an important contribution to the ore-forming fluids. Combined with the tectonic setting and previous isotopic geochemistry evidence, we conclude that the ore-deposit genesis is hydrothermal, sedimentary reformed, with multisources characteristics of ore-forming fluids.     

Trace elements in ocean ridge basalt glasses: implications for fractionations during mantle evolution and petrogenesis

Seven well-documented and fresh glassy selvages from ocean floor basalt pillows were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Os, Pd, Rb, Re, Sb, Se, Te, Tl, U and Zn. The samples came from active spreading centers in the Indian and Atlantic Ocean. Glasses from DSDP Leg 24, site 238 (Indian Ocean) have a somewhat peculiar trace element pattern, but this is thought to reflect secondary processes operating at shallow depth, not an anomalous source region in the mantle. Our data rather indicate that heterogeneities in the mantle are confined to the highly incompatible lithophile elements.Chemical fractionations during petrogenesis of tholeiitic basalts are discussed in the light of literature data for primitive peridotitic upper mantle nodules. (Ir, Os), Au, Pd, Ni and Re are strongly fractionated from each other in igneous processes; the unfractionated chondritic mantle pattern thus imposes firm constraints on mantle evolution models. The potentially chalcophile elements Ag, Cd, In and Zn do not behave differently from lithophile elements of the same valency and comparable ionic radius. Residual sulfides are not abundant enough to efficiently control the partitioning of these elements during basalt petrogenesis. However, the poor coherence of Tl to Rb and U in ocean floor basalts could point to retention of Tl by residual sulfides during depletion of the MORB source regions. Sb is strongly depleted in the source regions of ocean ridge basalts; most likely, it was present as a highly incompatible Sb⁵⁺ cation. The limited Rb/Cs fractionation in oceanic tholeiites, as opposed to continental tholeiites and acidic rocks, appears to reflect the low abundance of volatile constituents and hydrous silicates in normal ocean ridge basalts.     

贵州天桥铅锌矿床分散元素赋存状态及规律

利用电子探针(EPMA)、电感耦合等离子质谱(ICP-MS)等分析了天桥铅锌矿床矿石矿物中分散元素的含量、赋存状态及规律,结果表明分散元素在该矿床中含量达到了综合利用评价指标,有的甚至达到了工业品位(如Cd等);这些分散元素可能以类质同象的形式赋存在硫化物矿物中,其规律为Ga、Cd、In等赋存在闪锌矿中,Ge、Tl等赋存在方铅矿中,黄铁矿中分散元素富集低;在不同颜色闪锌矿中,Ga、Cd富集规律表现为浅色闪锌矿>中色闪锌矿>黑色闪锌矿,而Ge、Tl、In、Se富集表现出中色闪锌矿相对高于浅色及黑色闪锌矿;同标本中,不同颜色闪锌矿的Ge、In富集规律在还显示浅色闪锌矿>中色闪锌矿>黑色闪锌矿,而Ga、Tl、Cd、Se富集规律呈现中色闪锌矿相对高于浅色及黑色闪锌矿.Ga/In、Zn/Cd等参数指示出矿床成因类型可能为热液-沉积-改造.     

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.