A strong temperature effect on U/Ca in planktonic foraminiferal carbonates

Three planktonic foraminiferal species Globigerina bulloides, Neogloboquadrina pachyderma (d), and Globorotalia inflata collected from core-tops spanning 35° to 65°N in the North Atlantic were used for U/Ca and Mg/Ca and foraminiferal shell weight analyses. Except for U/Ca in G. bulloides calcified under warm conditions (>∼13 °C), U/Ca ratios in all three studied species increase with decreasing latitude and show strong positive correlations with Mg/Ca ratios. A dissolution effect on planktonic U/Ca is suggested by decreased shell weight and U/Ca and Mg/Ca ratios for shells from very deep water depth (>4.4 km) along the latitudinal transect. G. bulloides from down core samples in the North Atlantic show low U/Ca ratios during the last glacial and high ratios during the Holocene, similar to the Mg/Ca evolution trend. In general, our data indicate that the U incorporation into planktonic foraminiferal carbonates is strongly influenced by calcification temperature, although U/Ca in G. bulloides may be affected by seawater carbonate ion concentration under warm conditions and/or other factors.     

壳体大小对浮游有孔虫生物地球化学记录的影响

在浮游有孔虫壳体稳定同位素及Mg/Ca和Sr/Ca值的相关研究中,人们常因各种原因而选择不同粒径的壳体进行分析测试,而很少注意壳体大小可能导致研究结果的分歧。针对这一问题,本文分析了位于低纬度海区钻孔中不同粒径的Glo-bigerinoides ruber(白色,sensu stricto)和Pulleniatinaobliquiloculata壳体,结果表明G.ruber壳体的δ13C值受壳体大小的影响最为强烈,表现为正相关关系,不同粒径壳体的δ13C绝对平均差值可达0.48‰±0.12‰和0.25‰±0.09‰;P.obliquiloc-ulata400μm与315~400μm和250~315μm壳体Mg/Ca值的差异相当于1.8℃的海水温度;相对而言,G.ruberδ18O和Mg/Ca值以及P.obliquiloculataδ13C受壳体大小的影响较小,但它们的Sr/Ca值与壳体大小的关系不显著。本文推测,壳体大小相同时厚重的壳体可能成壳速度较快,相对优先吸收轻的同位素,且壳体Mg/Ca值可能更接近周围海水的水平。据此,本文认为较大个体P.obliquiloculata的壳体分泌可能与周围海水达到了平衡分馏。     

High resolution distribution of magnesium and strontium and the evaluation of Mg/Ca thermometry in Recent brachiopod shells

High resolution distribution of magnesium and strontium determined by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) are presented in this study for Recent brachiopod shells. The concentration of magnesium and strontium decreases in a similar fashion from the outer to inner regions of shells of rhynchonelliform species but remains unaltered in craniid brachiopods. In rhynchonelliform brachiopods with low-magnesium shells, there is a characteristic chemical profile with an abrupt decrease in magnesium concentration from the primary layer towards the secondary layer until it reaches a region in which the values are almost constant. In addition, there is a proportional relationship in magnesium concentration between primary and secondary layers. Both findings demonstrate the biological control in magnesium incorporation in rhynchonelliform brachiopods confirming previously reported findings. Calculated Mg/Ca ratios based on magnesium concentrations within the innermost region of the secondary layer show that rhynchonelliform brachiopods can record seawater temperature. This finding opens up the possibility of using Mg/Ca (palaeo) thermometry even within the context of biological control and the potential application of Mg/Ca ratios as a seawater temperature proxy in fossil brachiopods.     

Mg/Ca, Sr/Ca, and stable isotopes in modern and Holocene Protothaca staminea shells from a northern California coastal upwelling region

This study explores the potential of intertidal Protothaca staminea shells as high-resolution geochemical archives of environmental change in a coastal upwelling region. Mg/Ca and Sr/Ca ratios were analyzed by excimer laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) at sub-weekly temporal resolution in shells growing ∼1 mm per month. Growth patterns of a modern P. staminea shell from Humboldt Bay, California, collected in December 1999 made it possible to infer a lifespan from 1993 to 1998. Growth hiatuses in the shell may have excluded records of extreme events. Mg/Ca ratios appeared to be partly controlled by water temperature; the correlation coefficient between temperature and Mg/Ca was r = 0.71 in one of four growth increments. Significant year-to-year differences in the sensitivity of Mg/Ca to temperature in P. staminea could not be explained, however. Sr/Ca ratios appeared to be more closely related to shell growth rate. Oxygen isotopes, measured at 2-week temporal resolution in the same shell, did not show a clear relation to local temperature in summer, possibly because temperatures were higher and less variable at the King Salmon mudflat, where the shell was collected, than in the main channel of Humboldt Bay, where water properties were monitored. Negative shell δ¹³C values (<−0.5‰) marked spring and summer coastal upwelling events.The Mg contents of P. staminea midden shells dated to ∼3 ka and ∼9 ka were significantly lower than in the modern shell. This may have resulted from degradation of a Mg-rich shell organic matrix and precluded quantitative interpretation of the older high-resolution records. Elevated δ¹³C values in the ∼3 ka shell suggested that the individual grew in highly productive or stratified environment, such as a shallow coastal embayment or lagoon.     

Influences of organic matter and calcification rate on trace elements in aragonitic estuarine bivalve shells

A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction and shell calcification rates. The average organic content of whole C. amurensis shells is 19%. After treating whole powdered shells with an oxidative cleaning procedure to remove organic matter, shells contained on average 33% less total Mg and 78% less total Mn. Within our analytical uncertainty, Sr and Ba contents were unchanged by the removal of organic matter. These results show that aragonitic C. amurensis shells have a large component of non-lattice-bound Mg and Mn that probably contribute to the dissimilarity of [M]/Ca profiles among five same-sized shells. Non-lattice-bound trace elements could complicate the development and application of geochemical proxy relationships in bivalve shells. Because B, Ba and Sr occur exclusively in shell aragonite, they are good candidates for external proxy relationships. [M]/Ca ratios were significantly different in prismatic and nacreous aragonite and in two valves of the same shell that had different crystal growth rates. Some part of these differences can be attributed to non-lattice-bound trace elements associated with the organic fraction. The differences in [M]/Ca ratios were also consistent with the calcification rate-dependent ion transport model developed by Carré et al. [Carré M., Bentaleb I., Bruguier O., Ordinola E., Barrett N. T. and Fontugne M. (2006) Calcification rate influence on trace element concentrations in aragonitic bivalve shells: evidences and mechanisms. Geochim. Cosmochim. Acta70, 4906-4920] which predicts that [M]/Ca ratios increase as calcification rates increase and Ca²⁺ channel specificity decreases. This result, in combination with the possibility that there were ontogenetic variations in growth rates among individuals younger than 2 years, underscores the need to develop an independent age model for C. amurensis shells. If growth-rate effects on lattice-bound [M]/Ca ratios can be constrained, it may yet be possible to develop high-resolution geochemical proxies for external solution chemistry in low-salinity regions of SFB.     

The impact of solution chemistry on Mytilus edulis calcite and aragonite

Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.     

Environmental and biological controls on elemental (Mg/Ca, Sr/Ca and Mn/Ca) ratios in shells of the king scallop Pecten maximus

The relationship between potential elemental proxies (Mg/Ca, Sr/Ca and Mn/Ca ratios) and environmental factors was investigated for the bivalve Pecten maximus in a detailed field study undertaken in the Menai Strait, Wales, U.K. An age model constructed for each shell by comparison of measured and predicted oxygen-isotope ratios allowed comparison on a calendar time scale of shell elemental data with environmental variables, as well as estimation of shell growth rates. The seasonal variation of shell Mn/Ca ratios followed a similar pattern to one previously described for dissolved Mn²⁺ in the Menai Strait, although further calibration work is needed to validate such a relationship. Shell Sr/Ca ratios unexpectedly were found to co-vary most significantly with calcification temperature, whilst shell Mg/Ca ratios were the next most significant control. The temporal variation in the factors that control shell Sr/Ca ratios strongly suggest the former observation most likely to be the result of a secondary influence on shell Sr/Ca ratios by kinetic effects, the latter driven by seasonal variation in shell growth rate that is in turn influenced in part by seawater temperature. P. maximus shell Mg/Ca ratio to calcification temperature relationships exhibit an inverse correlation during autumn to early spring (October to March-April) and a positive correlation from late spring through summer (May-June to September). No clear explanation is evident for the former trend, but the similarity of the records from the three shells analysed indicate that it is a real signal and not a spurious observation. These observations confirm that application of the Mg/Ca proxy in P. maximus shells remains problematic, even for seasonal or absolute temperature reconstructions. For the range of calcification temperatures of 5-19 °C, our shell Mg/Ca ratios in P. maximus are approximately one-fourth those in inorganic calcite, half those in the bivalve Pinna nobilis, twice those in the bivalve Mytilus trossulus, and four to five times higher than Mg/Ca ratios in planktonic and benthonic foraminifera. Our findings further support observations that Mg/Ca ratios in bivalve shell calcite are an unreliable temperature proxy, as well as substantial taxon- and species-specific variation in Mg incorporation into bivalves and other calcifying organisms, with profound implications for the application of this geochemical proxy to the bivalve fossil record.     

青藏高原中部色林错中晚全新世以来古气候变化特征

色林错位于青藏高原中部印度季风和西风环流的过渡地带，同时受西风环流和印度季风系统控制，是研究二者进退变化特征的理想场所。本文利用色林错SL 1钻孔中介形虫 Limnocythere inopinata 的丰度及其壳体微量元素Mg/Ca和Mn/Ca比值重建了色林错5. 3 ka BP以来的古气候环境变化特征。5. 3~2. 9 ka BP， L. inopinata 丰度较小，壳体的低Mg/Ca比值和高Mn/Ca比值表明此阶段气候偏冷湿；2. 9~1. 8 ka BP， L. inopinata 丰度较前一阶段增加，壳体Mg/Ca比值略有增长但仍为低值表明气温虽然有所回升但仍然较低，Mn/Ca比值较前一阶段明显降低，指示湖泊水位下降；1. 8 ka BP至今， L. inopinata 丰度达到最大，壳体的高Mg/Ca和Mn/Ca比值指示湖泊温度和水位均呈显著的上升趋势。通过与西风区、过渡区以及印度季风区其他湖泊的环境沉积记录对比，本文认为青藏高原中部地区在中全新世晚期主要受西风环流影响，气温较低，西风带来大量水汽使得湖面呈扩张趋势；而到晚全新世西风环流逐渐北撤，色林错受季风影响更大，季风带来的降水和气温升高导致的冰川融水增加与色林错水位上升有密切关系。     

利用富钴结壳碳酸盐基岩有孔虫矿物标型重建古海洋温度

重建古海洋海表温度(SST),是研究地质历史时期气候变化控制过程的关键。组成有孔虫化石的矿物Mg/Ca值是海水温度的可靠代用指标,是重建古海洋SST的一个非常好的手段。麦哲伦海山区的富钴结壳和基岩中普遍存在有孔虫化石,这对重建该区的SST有重要意义。利用LA-ICP-MS测得西太平洋麦哲伦海山区富钴结壳碳酸盐基岩中8颗浮游有孔虫化石Globigerinoides sacculifer的Mg/Ca值为3.84±0.36(mmol/mol),通过线性公式:T(℃)=2.898Mg/Ca(mmol/mol)+13.76及已有的定年数据,得到0.91Ma±西太平洋麦哲伦海山区海表温度为24.9+1.1/-1.0℃,未能检索到前人关于该区0.91Ma±前海表温度数据。     

Li/Ca ratios of ostracod shells at Lake Qinghai, NE Tibetan Plateau, China: a potential temperature indicator

Acquiring continuous and high-resolution natural records in recent 2,000?years is the hot issue in the palaeoclimate research. Recent studies revealed that Li/Ca and Mg/Li ratio of carbonate is a potential tracer of past environmental changes in the oceans, and is seldom applied for palaeoclimate reconstruction in lakes. To make full understanding of the potential of Li/Ca ratios of carbonates in lakes, Li/Ca ratios of monospecific ostracod shell Eucypris inflate with similar size in the lacustrine sediment core from Lake Qinghai, NE Tibetan Plateau have been analysed for the first time. Single species can effectively avoid the interspecies effects. In combination with the sedimentation rate that existed, data derived from ²¹⁰Pb and ¹³⁷Cs, downcore variations of Li/Ca ratios of ostracod shells during the past 800?years in Lake Qinghai have been reconstructed successfully. By comparing Li/Ca ratios and temperature inferred from meteorological records and tree ring widths in Dulan and Qilianshan in adjacent regions, Li/Ca ratios of ostracod shells negatively correlate with temperature. Higher temperature corresponds with lower Li/Ca ratios, and vice versa, indicating that Li/Ca ratio of ostracod shells is an effective indicator for temperature variations. Therefore, ongoing in-depth investigation using Li/Ca ratios of carbonates in more lakes to further reveal its palaeotemperature implications would be deserved.     

洞穴次生碳酸盐沉积的Mg/Ca与Sr/Ca比值研究进展——兼论洞穴次生沉积物Mg/Ca与Sr/Ca的影响机制

微量元素是岩溶洞穴沉积中非常重要的一类古气候环境替代指标,为近20年来国内外的一个研究热点。总结前人的研究,主要取得了以下一些重要认识:（1）洞穴上覆土壤 和围岩是洞穴次生碳酸盐沉积Mg、Sr的主要来源;（2）Mg/Ca与Sr/Ca能够指示气候环境变化,但需结合其它指标综合考虑。（3）洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca受多种气候环境因素（包括土壤和围岩的组成和性质、水-岩相互作用、先期碳酸盐沉积、分配系数等）影响,其古气候环境指示意义具有多解性;（4）矿物结晶作用对Mg/Ca与Sr/Ca有一定的影响,特别是文石在向方解石转变的过程中容易丢失Mg、Sr,此外,杂质的混入也将抑制Mg、Sr进入方解石,从而引起洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca比值的变化。今后应进一步加强对石笋中这些微量元素的影响机制研究,尤其是对一些影响因素与微量元素含量变化之间的定量关系进行探讨。      

The impact of salinity on the Mg/Ca and Sr/Ca ratio in the benthic foraminifera Ammonia tepida: Results from culture experiments

Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ¹⁸O signal measured on the same material, to calculate the δ¹⁸O_w, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor D_Sr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in D_Mg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The D_Sr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.     

Benthic foraminiferal Mg/Ca-paleothermometry: a revised core-top calibration

Core-top samples from different ocean basins have been analyzed to refine our current understanding of the sensitivity of benthic foraminiferal calcite magnesium/calcium (Mg/Ca) to bottom water temperatures (BWT). Benthic foraminifera collected from Hawaii, Little Bahama Bank, Sea of Okhotsk, Gulf of California, NE Atlantic, Ceara Rise, Sierra Leone Rise, the Ontong Java Plateau, and the Southern Ocean covering a temperature range of 0.8 to 18°C were used to revise the Cibicidoides Mg/Ca-temperature calibration. The Mg/Ca-BWT relationship of three common Cibicidoides species is described by an exponential equation: Mg/Ca = 0.867 ± 0.049 exp (0.109 ± 0.007 × BWT) (stated errors are 95% CI). The temperature sensitivity is very similar to a previously published calibration. However, the revised calibration has a significantly different preexponential constant, resulting in different predicted absolute temperatures. We attribute this difference in the preexponential constant to an analytical issue of accuracy. Some genera, notably Uvigerina, show apparently lower temperature sensitivity than others, suggesting that the use of constant offsets to account for vital effects in Mg/Ca may not be appropriate. Downcore Mg/Ca reproducibility, as determined on replicate foraminiferal samples, is typically better than 0.1 mmol mol⁻¹ (2 S.E.). Thus, considering the errors associated with the Cibicidoides calibration and the downcore reproducibility, BWT may be estimated to within ±1°C. Application of the revised core-top Mg/Ca-BWT data to Cenozoic foraminiferal Mg/Ca suggests that seawater Mg/Ca was not more than 35% lower than today in the ice-free ocean at 50 Ma.     

万年尺度下钙华的古环境重建检验——以青海冰凌山为例

采用钙华中微量元素进行古气候环境重建为近年来国内外研究热点。前人研究成果主要为小时间尺度古气候环境重建,因微量元素的影响机制及地区间差异性问题,可能存在未知因素影响稀土元素含量及Mg/Ca、Mg/Sr比值,从而导致解译的古气候环境意义失真。以位于青海省格尔木地区的达布逊湖达1井孢粉谱图与青藏高原湖区变化谱图为参照对象,对青海省平安县三合镇东北冰凌山万年尺度下钙华的古环境重建方法进行了检验,结果表明:1)冰凌山泉华台地沉积环境相对稳定,提供冰凌山钙华物质来源的地下水长期处于接受来自地壳深部CO2补给的偏酸性条件下;2)所采集钙华样品除P04点外,均具有相同的物质来源和形成过程;3)万年尺度下,用钙华中的稀有元素总量重建古气温方法可行,且稀有元素总量与古气温呈负相关关系;4)采用Mg/Ca、Mg/Sr比值重建古降水环境应区分钙华成因类型,表生钙华Mg/Ca、Mg/Sr比值与古降水呈现负相关,而内生钙华Mg/Ca、Mg/Sr比值与古降水呈现正相关.     

Li,Sr, Mg,and Na in foraminiferal calcite shells from laboratory culture,sediment traps,and sediment cores

Constant-temperature laboratory culture experiments of the planktonic foraminiferal species Globigerinoides sacculifer (Brady) suggest that the ratios of Li and Sr to Ca in the shells are a function of these ratios in the culture solutions. $\text{Mg}\text{Ca}$ and $\text{Na}\text{Ca}$ in the shells did not vary with changes of these ratios in the culture solution. These are the first direct determinations of the relationship between foraminiferal shell chemistry and solution composition.The possibility of temperature dependence for the minor elemental composition of foraminiferal shells was also investigated in the laboratory and by analysis of several planktonic and one benthic foraminiferal species from sediment trap and sediment core samples. The $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios in the natural samples roughly correlate with calcification temperature, whereas differences in the Li/Ca ratios are small and not systematically related to temperature. However, laboratory culture experiments at 20°C and 30°C showed no variation in the $\text{Li}\text{Ca}$, $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios with calcification temperature for the planktonic foraminifera G. sacculifer and Orbulina universa. Therefore, observed differences in the $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios for the sediment trap and core foraminiferal samples cannot be ascribed to direct effects of calcification temperature, but may be due to some other environmental factor which is correlated with temperature.     

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg⁻¹. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants’ roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils.     

雪玉洞岩溶地下水、地表水Ca2+、Mg2+、Sr2+变化特征研究

通过2011年对重庆丰都雪玉洞洞内滴水和地下河河水,上覆岩层中出露的表层岩溶泉水和雪玉洞附近龙河河水等不同类型水中Ca2+、Mg2+、Sr2+浓度及Mg/Ca、Sr/Ca值的研究,发现不同水的Ca2+、Mg2+、Sr2+随外界降水条件的改变而出现明显变化。表层岩溶泉水Ca2+变化能够敏感反应外界降水条件改变,滴水对外界降雨的反应滞后接近1个月,地下河Ca2+可以反应雨季和旱季的变化,地表河水Ca2+全年比较稳定,但是对特殊干旱天气有显著响应。2011年不同类型水的Mg2+、Sr2+全年变化趋势基本一致,在降水较多的3、5、10月呈低值,在其他降水较少的月份浓度相对较高。各离子的这种变化特征主要是受到稀释效应、CO2效应以及所在地层的岩性的影响。雪玉洞不同类型水的Mg/Ca、Sr/Ca值呈现出滴水>地表河>地下河>表层岩溶泉的特点,反映出不同类型水在含水介质中滞留时间的长短,并且Mg/Ca、Sr/Ca值在降水较多的月份降低,在降水较少的月份升高;受碳酸钙的前期沉淀和运移路径差异的影响,不同类型水的Mg/Ca、Sr/Ca值变化稍有不同。因此,不同类型水的离子变化及其比值对外界降水条件变化的响应特征和时间的不同,决定了在利用元素及其比值反映外界环境变化时也要区别对待。      

Seasonal changes of fulvic acid,Ca and Mg concentrations of water samples collected above and in the Béke Cave of the Aggtelek karst system (Hungary)

Magnesium and Ca concentration ratios, fulvic acid content, total dissolved inorganic carbon (DIC) and pH were determined in seepage water and drip water samples collected during one seasonal cycle between June 2000 and May 2001 above and in the Béke Cave of Aggtelek (Hungary). Seepage water samples were collected at 0.5 and 7 m below ground level from an observation point situated above the cave. Drip water was collected 40 m underground from a group of stalactites. The fulvic acid concentrations were determined by fluorescence spectrometry after pre-concentration on a XAD-8 chromatographic column. Calcium and Mg concentrations were measured by inductively coupled plasma atomic-emission spectrometry. DIC was determined with a CO₂ – selective electrode. DIC values increased and the fulvic acid concentrations and Mg and Ca concentration ratios, generally, decreased with depth. The highest flux of fulvic acid was observed in spring. The fulvic acid flux increased by a factor of 2.6–3.6 and 1.4 for groundwater and drip water, respectively, compared with those registered in the winter samples. The variations in the Ca, Mg and fulvic acid concentrations of the seepage and drip water samples relate to the variable drip rate. The results revealed that there is a strong correlation between the daily average surface temperature, daily amount of precipitation and drip water rate registered in the cave.     

Interindividual variability and ontogenetic effects on Mg and Sr incorporation in the planktonic foraminifer Globigerinoides sacculifer

In order to investigate the interindividual and ontogenetic effects on Mg and Sr incorporation, magnesium/calcium (Mg/Ca) and strontium/calcium (Sr/Ca) ratios of cultured planktonic foraminifera have been determined. Specimens of Globigerinoides sacculifer were grown under controlled physical and chemical seawater conditions in the laboratory. By using this approach, we minimised the effect of potential environmental variability on Mg/Ca and Sr/Ca ratios. Whereas temperature is the overriding control of Mg/Ca ratios, the interindividual variability observed in the Mg/Ca values contributes 2-3 °C to the apparent temperature variance. Interindividual variability in Sr/Ca ratios is much smaller than that observed in Mg/Ca values. The variability due to ontogeny corresponds to −0.43 mmol/mol of Mg/Ca ratio per chamber added. This translates into an apparent decrease of ∼1 °C in Mg/Ca-based temperature per ontogenetic (chamber) stage. No significant ontogenetic effect is observed on Sr incorporation. We conclude that the presence of a significant ontogenetic effect on Mg incorporation can potentially offset Mg/Ca-based temperature reconstructions. We propose two new empirical Mg/Ca-temperature equation based on Mg/Ca measurements of the last four ontogenetic (chamber) stages and whole foraminiferal test: Mg/Ca = (0.55(±0.03) − 0.0002(±4 × 10⁻⁵) MSD) e^0.089T and, Mg/Ca = (0.55(±0.03) − 0.0001(±2 × 10⁻⁵) MSD) e^0.089T, respectively, where MSD corresponds to the maximum shell diameter of the individual.     

中祁连西段巴嘎德尔基岩体LA-ICP-MS锆石U-Pb年龄及地质意义

巴嘎德尔基岩体位于中祁连山西段的野马南山地区,主要由钾长花岗岩和二长花岗岩组成.LA-ICP-MS锆石U-Pb测年表明,巴嘎德尔基岩体侵位年龄为462.9±1.4Ma.该岩体地球化学方面表现出强过铝、高K、K/Na,低Mg、Fe、Ca的主量元素特征,并富集K、Rb、Ba、Th,亏损Zr、Hf、Y、Yb等微量元素,轻稀土富集,弱的Eu负异常.在微量元素判别图解上,所有岩石投影点均落入同碰撞区域.结合区域地质背景,认为巴嘎德尔基岩体是加里东造山作用晚期陆陆碰撞的产物.