树轮稳定同位素记录:进展、问题及展望

树轮稳定同位素比率(δ13 C、δ18O 和δD)变化与树木生长季的气候和环境条件密切相关。控制实验表明, 树轮稳定同位素比率变化可较好地记录树木叶片气孔活动、水分来源、水分利用效率等相关信息, 已成为古气候和全球变化生态学研究的重要代用指标和手段之一。树轮稳定同位素记录能够较好地保留低频气候环境变化信息, 与年轮宽度相结合, 可有效地进行区域古气候重建和全球变化生态学方面的研究。文章综述了树轮稳定同位素的分馏机理及其发展, 系统阐述和评价了利用树轮稳定同位素指标进行古气候和古环境的相关研究成果, 并指出树轮稳定同位素研究在中国未来亟须着重发展的方向。     

锑的地球化学行为以及锑同位素研究进展

锑被广泛用于生产各种阻燃剂、玻璃、橡胶、颜料、陶瓷、半导体原件等。锑在火成岩中属于分散元素,但可以富集在沉积岩中（如深海黏土、页岩及碎屑岩）。锑常出现在与辉长质深成岩有关的岩浆硫化物矿床、与花岗岩有关的硫化物矿床、碎屑岩-碳酸岩赋矿的钨-锑-汞层控矿床及热液铅锌矿床中。目前高精度锑同位素的分析测试方法已基本成熟,即酸溶、阳离子树脂交换柱结合硫醇棉纤维法或阴阳离子交换柱法分离富集锑、氢化物发生器MC-ICP-MS测定锑同位素。仪器的质量歧视校正通常采用标样-样品匹配法、In内标法和Sn内标法。不同地质储库端元的锑同位素组成变化较大（达18‱）,海水为～3.7‱,硅酸岩为0.9‱～2.9‱,硫化物（辉锑矿、闪锌矿、黄铁矿、白铁矿）为-1.9‱～16.9‱。且来自不同国家的辉锑矿具有不同的锑同位素组成,不同产地玻璃的锑同位素组成也不同。锑同位素在氧化还原过程（或硫化物沉淀）和无机吸附过程会发生明显分馏,分别达～9‱和～4‱。因此,锑同位素有可能作为一种灵敏的地球化学示踪剂,对示踪成矿物质来源、刻画与氧化还原等过程有关的成矿过程和探讨矿床形成机理、矿区重金属锑污染的治理以及考古等方面具有重要指示作用。     

Elemental and isotopic carbon and nitrogen records of organic matter accumulation in a Holocene permafrost peat sequence in the East European Russian Arctic

A peat deposit from the East European Russian Arctic, spanning nearly 10 000 years, was investigated to study soil organic matter degradation using analyses of bulk elemental and stable isotopic compositions and plant macrofossil remains. The peat accumulated initially in a wet fen that was transformed into a peat plateau bog following aggradation of permafrost in the late Holocene (～2500 cal a BP). Total organic carbon and total nitrogen (N) concentrations are higher in the fen peat than in the moss‐dominated bog peat layers. Layers in the sequence that have lower concentrations of total hydrogen (H) are associated with degraded vascular plant residues. C/N and H/C atomic ratios indicate better preservation of organic matter in peat material dominated by bryophytes as opposed to vascular plants. The presence of permafrost in the peat plateau stage and water‐saturated conditions at the bottom of the fen stage appear to lead to better preservation of organic plant material. δ¹⁵N values suggest N isotopic fractionation was driven primarily by microbial decomposition whereas differences in δ¹³C values appear to reflect mainly changes in plant assemblages. Positive shifts in both δ¹⁵N and δ¹³C values coincide with a local change to drier conditions as a result of the onset of permafrost and frost heave of the peat surface. This pattern suggests that permafrost aggradation not only resulted in changes in vegetation but also aerated the underlying fen peat, which enhanced microbial denitrification, causing the observed ¹⁵N‐enrichment. Copyright © 2012 John Wiley & Sons, Ltd.     

Climate change during the past 1000 years: a high‐temporal‐resolution multiproxy record from a mire in northern Finland

We present a record of peatland development in relation to climate changes and human activities from the Palomaa mire, a remote site in northern Finland. We used fine‐resolution and continuous sampling to analyse several proxies including pollen (for vegetation on and around the mire), testate amoebae (TA; for mire‐wetness changes), oxygen and carbon isotopes from Sphagnum cellulose (δ¹⁸O and δ¹³C; for humidity and temperature changes), peat‐accumulation rates and peat‐colour changes. In spite of an excellent accumulation model (30 ¹⁴C dates and estimated standard deviation of sample ages <1 year in the most recent part), the potential to determine cause–effect (or lead–lag) relationships between environmental changes and biotic responses is limited by proxy‐specific incorporation processes below the actively growing Sphagnum surface. Nevertheless, what emerges is that mire development was closely related to water‐table changes rather than to summer temperature and that water‐table decreases were associated with increasing peat‐accumulation rates and more abundant mire vegetation. A rapid fen‐to‐bog transition occurred within a few years around AD 1960 when the water table decreased beyond the historical minimum, supporting the notion that mires can rapidly shift into bogs in response to allogenic factors. Copyright © 2012 John Wiley & Sons, Ltd.     

莱州湾南岸卤水的稳定同位素与地球化学特征

莱州湾南岸卤水的开发利用始于20世纪50年代,如今卤水的含盐量比海水高出3～6倍。本文采用稳定同位素和水化学分析来鉴定卤水的盐分来源,为此在研究区内采集了9件卤水样品,采样井深度为30～80m。首先根据同位素盐效应,对卤水的δD和δ~(18)O值进行了校正。校正后的δD和δ~(18)O值关系图表明卤水的水分子来源于大气降水,而不是海水。δ~(18)O—Cl~-和Br~-—Cl~-关系表明卤水的盐分不同于海水蒸发的余留水。根据化学分水岭原理,卤水的Ca~(2+)/SO_(-4)~2和Ca~(2+)/Mg~(2+)值演化提示溶解盐起源不是蒸发的海水卤水。其它化学成分关系也证实了卤水的盐分源于海水蒸发盐的反复溶解。本研究说明卤水样品与海水盐分有关,但是与海水的水分子无关。     

末次间冰期以来渭南黄土剖面地球化学指标所反映的古气候变化

渭南剖面由全新世土壤Ｓ０，末次冰期黄土Ｌ１及末次间期古土壤Ｓ１和组成。其中，Ｌ１可以进一步划分为三层黄土和两层弱发育的土壤；Ｓ１由三层土壤组成。碳酸盐，游离铁及有机质含旺在渭南剖面上的变化表明上述化学成分可以用作缺气候的替代性指标，并能反映古气候的变化。     

论季风气候对我国雨水同位素组成的影响

根据我国积累的雨水同位素组成资料，讨论季风气候对雨水同位素组成的影响。受季风影响的地区、与温度效应预测的相反，夏季雨水δ值偏低，雨水的δ值并不一定和降水量有关。夏季风期间暖湿汽团在亚洲登陆前，已经历较大的同位素分馏，故明显贫重同位素。用夏冬两季雨水平均δ＾１８Ｏ之差讨论了雨水δ值受季风气候影响的程度。我国东部及云南和西藏南部受季风影响最为明显，而新疆则在影响范围之外，根据氘过剩值探讨了夏冬季风期间     

Constraining flow paths of saline groundwater at basin margins using hydrochemistry and environmental isotopes: Lake Cooper,Murray Basin,Australia

Solutes in saline groundwater (total dissolved solids up to 37 000 mg/L) in the Lake Cooper region in the southern margin of the Riverine Province of the Murray Basin are derived by evapotranspiration of rainfall with minor silicate, carbonate and halite dissolution. The distribution of hydraulic heads, salinity, percentage modern carbon (pmc) contents, and Cl/Br ratios imply that the groundwater system is complex with vertical flow superimposed on lateral flow away from the basin margins. Similarities in major ion composition, stable (O, H, and C) isotope, and ⁸⁷Sr/⁸⁶Sr ratios between groundwater from the shallower Shepparton Formation and the deeper Calivil – Renmark aquifer also imply that these aquifers are hydraulically interconnected. Groundwater in the deeper Calivil – Renmark aquifer in the Lake Cooper region has residence times of up to 25 000 years, implying that pre-land-clearing recharge rates were <1 mm/y. As in other regions of the Murray Basin, the low recharge rates account for the occurrence of high-salinity groundwater. Shallow (<20 m) groundwater yields exclusively modern ¹⁴C ages and shows a greater influence of evaporation over transpiration. Both these observations reflect the rise of the regional water-table following land clearing over the last 200 years and a subsequent increase in recharge to 10 – 20 mm/y. The rise of the regional water-table also has increased vertical and horizontal hydraulic gradients that may ultimately lead to the export of salt from the Lake Cooper embayment into the adjacent fresher groundwater resources.     

Petrography and geochemistry of septarian carbonate concretions from the Boom Clay Formation (Oligocene,Belgium)

The septarian carbonate concretions from the Boom Clay (Belgium) consist mainly of authigenic minerals such as micrite ( 70% bulk volume) and pyrite framboids ( 3%). These mineral phases occur between detrital grains and fossils. The septarian cracks are lined with calcite, which is sometimes covered with pyrite. The preservation of delicate sedimentological features in the concretion matrix (hardly compacted faecal pellets, burrows and uncrushed shells) points to an early origin of the concretions. Systematic geochemical variations from concretion centre to edge suggest that growth continued during shallow burial. The13C values (–17.5 to –20.5) of the concretionary carbonate show that bacterial sulphate-reduction processes were dominant. Sulphate-reduction-derived HCO3- was diluted by marine-related HCO3-, derived from dissolved bioclasts. A slight enrichment in 13C during growth is caused by the decreasing influence of sulphate reduction because of the progressive closure of the diagenetic system due to shallow-burial compaction. The 18O values (–0.5 to +1.0) of the concretionary carbonate point to a marine origin. The slightly 18O-depleted signature with respect to time-equivalent marine-derived carbonate relates to the incorporation of an 18O-depleted component, originating from sulphate and organic matter. The slight decrease in 18O during growth relates to an increasing influence of this component and to a decreasing influence of seawater-derived oxygen during early diagenesis.     

Aragonite stromatolitic buildups from Santorini (Aegean Sea,Greece): Geochemical and palaeontological constraints of the caldera palaeoenvironment prior to the Minoan eruption (ca 3600 yr bp)

The pyroclastic deposits of the Minoan eruption (ca 3600 yr bp ) in Santorini contain abundant xenoliths. Most of these deposits are calcareous blocks of laminated‐botryoidal, stromatolite‐like buildups that formed in the shallow waters of the flooded pre‐Minoan caldera; they consist of (i) light laminae, of fibrous aragonite arranged perpendicular to layering, and (ii) dark laminae, with calcified filaments of probable biological origin. These microstructures are absent in the light laminae, suggesting a predominant inorganic precipitation of aragonite on substrates probably colonized by microbes. Internal cavities contain loose skeletal grains (molluscs, ostracods, foraminifera and diatoms) that comprise taxa typical of shallow marine and/or lagoon environments. Most of these forms are typical of warm water environments, although no typical taxa from hydrothermal vents have been observed. Past gasohydrothermal venting is recorded by the occurrence of barite, pyrolusite and pyrite traces. The most striking features of the stable isotopic data set are: (i) an overall wide range in δ¹³C_PDB (0·16 to 12·97‰) with a narrower variation for δ¹⁸O_PDB (?0·23 to 4·33‰); and (ii) a relatively uniform isotopic composition for the fibrous aragonite (δ¹³C = 12·40 ± 0·43‰ and δ¹⁸O = 2·42 ± 0·77‰, n = 21). The δ¹³C and δ¹⁸O values from molluscs and ostracods display a covariant trend, which reflects a mixing between sea water and a fluid influenced by volcano‐hydrothermal activity. Accordingly, ⁸⁷Sr/⁸⁶Sr from the studied carbonates (0·708758 to 0·709011 in fibrous aragonite and 0·708920 to 0·708991 in molluscs) suggests that the aragonite buildups developed in sea water under the influence of a hydrothermal/volcanic source. Significant differences in trace elements have been detected between the fibrous aragonite and modern marine aragonite cements. The caldera water from which the fibrous aragonite crusts formed received an input from a volcano‐hydrothermal system, probably producing diffuse venting of volcanogenic CO₂ gas and of a fluid enriched in Ca, Mn and Ba, and depleted in Mg and probably in Sr.     

硅酸盐化学风化强度评估的沉积物指标与方法研究进展*

风化作用是源-汇沉积体系中的重要环节,气候、构造、地形、植被和岩性在不同程度上控制着地表硅酸盐化学风化,量化硅酸盐化学风化强度有助于开展全球性的实例研究对比。本研究归纳总结了基于碎屑沉积物的化学风化强度指标,包括岩石学和矿物学指标、元素地球化学指标和非传统稳定同位素指标,并指出了指标在应用中存在的问题。这些指标中:砂质沉积物骨架颗粒组成、粉砂级碎屑的矿物组成和矿物表面结构特征从矿物组成和结构上直观地反映了化学风化强度,运用不多但值得关注;黏土矿物组合和主微量元素指标如CIA、Rb/Sr、α^AlE等在实例研究中运用广泛,同时也显现出易受物源和水动力分选影响等弊端;新近开发的利用锂、硼、钾、镁、硅等同位素示踪化学风化强度的方法具有广阔的应用前景,同位素的分馏机理有待完善。源-汇体系中的其他过程如物源供给、水动力分选、成岩作用、再旋回作用、成土作用、物理淋滤和生物利用等会影响化学风化指标的使用效果,通过多指标的综合运用和相互验证,可以有效提升化学风化强度评估的准确性。     

Paleoclimate of Southwestern China for the Past 50,000 yr Inferred from Lake Sediment Records

Long sediment cores (12.5 and 13.5 m) from two lakes in Yunnan Province were used to infer the paleoclimate of southwest China over the past 50,000 yr. During the Holocene and marine isotope stage (MIS 3), bio-induced carbonate precipitation and organic matter (OM) production was high, suggesting warm temperatures and high primary productivity. In contrast, sediment inorganic carbon (IC) and organic carbon (OC) concentrations were low in last glacial deposits from 38,000 to 12,000 cal yr B.P., indicating cool temperatures and low productivity. The 50,000-yr record has alternating peaks of carbonate and coarse-grain (>38 μm) quartz that reflect warm, moist interglacial or interstadial conditions alternating with cold, dry glacial or stadial conditions, respectively. Spectral analysis of the carbonate and quartz signals reveals power concentrated at periods of 7200 and 8900 cal yr, respectively, that may reflect a nonlinear climate response to precessional forcing at a time of reduced eccentricity modulation (McIntyre and Molfino, 1996). Oxygen isotope values of calcite from Yunnan lake cores indicate the summer monsoon was weak during the last glaciation from 50,000 to 12,000 cal yr B.P. The summer monsoon intensified between 12,000 and 8000 cal yr B.P., but weakened gradually in response to insolation forcing during the mid-to-late Holocene. Our results support the Overpeck et al. (1996) model that posits a weak summer monsoon during the last glaciation that responded nonlinearly to insolation forcing when its intensity was affected by Eurasian snow cover and ice-sheet extent. The summer monsoon intensified and responded linearly to seasonal insolation forcing in the Holocene when ice volume diminished.     

石碌钴-铜矿床流体包裹体和稳定同位素特征及成因

海南石碌钴-铜矿体赋存于石碌群第六层的下段,即介于铁矿体与石碌群第五层片岩之间的含钴-铜层位中,容矿岩石主要为白云岩、透辉石透闪石化白云岩。钴-铜矿床的形成经历了海底喷溢沉积期、石英-硫化物期(热液期)和表生期。海底喷溢沉积期石英包裹体均一温度变化于112~205℃,多集中在130~205℃;盐度w(NaCl_eq)为1.74%~6.59%;密度变化于0.88~0.95 g/cm³。温度范围与很多古代沉积喷流矿床及正在活动的海底热液成矿作用的温度相似,盐度低于曾报道的多数沉积喷流矿床的流体包裹体盐度值, 但与那些同为低密度成矿流体的喷流沉积矿床极为相近。海底喷溢沉积期形成的硬石膏δ³⁴S值为+21.4‰~+21.8‰,平均值为+21.6‰,强烈富集重硫,硬石膏δ³⁴S值代表着新元古代石碌群沉积时海水的δ³⁴S值。石英-硫化物期石英、白云石和方解石均一温度多集中在170~270℃;盐度w(NaCl_eq)为1%~7%;密度变化于0.88~0.95 g/cm³。成矿流体属于中温低盐度流体。石英-硫化物期成矿流体δD值为-63‰~-83‰,成矿流体δ¹⁸O_水值变化于1.3‰~6.8‰之间,指示成矿流体来源于岩浆,成矿后期有大气降水的加入。石英-硫化物期硫化物δ³⁴S值为+8.1‰~+21.2‰,硫源来源于石碌群中蒸发岩的溶解作用。石碌钴-铜矿床属中温热液充填交代矿床,与矿床周围花岗质岩浆活动有关。