再探温跃层有孔虫B/Ca与温度和[CO32-]的依赖性及其在24 ka以来热带西太平洋次表层碳酸盐系统重建中的应用

The B/Ca ratio of planktonic foraminifer shells has been used as a proxy for reconstructing past ocean carbonate chemistry. However, recent studies have revealed significant uncertainties associated with this proxy, such as whether seawater temperature or [ CO_3~(2-)] is the dominant control on the partition coefficient(K_D) of planktonic foraminiferal B/Ca. To address these uncertainties and thus improve our understanding of the planktonic foraminiferal B/Ca proxy, we analysed B/Ca ratios in the tests of Neogloboquadrina dutertrei(300–355 μm) and Pulleniatina obliquiloculata(355–400 μm) in surface sediment samples from the tropical western Pacific and South China Sea. The relationship between these B/Ca ratios and bottom water calcite saturation states(Δ[ CO_3~(2-)]) is weak, thus suggesting only a small dissolution effect on the B/Ca of the two species. The correlation coefficients(R~2) between the B/Ca ratios of N. dutertrei and P. obliquiloculata and environmental parameters(e.g., temperature, salinity, phosphate, DIC and ALK) in the tropical western Pacific and South China Sea are not high enough to justify using B/Ca ratios as a palaeoenvironmental proxy in the study areas. The significant correlation between K_D values of N. dutertrei and P. obliquiloculata and carbonate system parameters(e.g.,[ CO_3~(2-)], DIC, ALK, pH and [ HCO_3~-]) in the study area reflect chemical links between the K_D denominator and these variables. Based on our surface sediment calibration, an empirical relationship between the K_D of N.dutertrei and temperature is proposed in the tropical western Pacific. We also generated a record of B/Ca ratios in N. dutertrei(300–355 μm) from Core MD06-3052 in the tropical western Pacific over the past 24 ka to evaluate the application of the revised B/Ca proxy method. Based on the reconstructed empirical relationship for B/Ca and subsurface seawater ALK, we estimated subsurface seawater carbonate system parameters in the tropical western Pacific since 24 ka. In general, the estimated subsurface seawater pH and [ CO_3~(2-)] show an increase with time, and the record of subsurface seawater pCO_2 shows a decrease with time, in the tropical western Pacific over the past 24 ka. The consistent trends in subsurface seawater pCO_2 and opal flux during deglaciation may imply that the reported increase in subsurface water pCO_2 in the study area was promoted by enhanced upwelling in the Southern Ocean.     

The response of ostracod shell chemistry to seasonal change in a Mediterranean freshwater spring environment

We established the relationships between water chemistry changes in a pool fed by a permanent spring and seasonal variations in trace-element contents (Sr & Mg) in the shells of the ostracod species Herpetocypris intermedia, based on monthly collections of ostracod and water samples. The water chemistry of the investigated pool (Maïques, Valëncia, Spain) was dominated by calcium and bicarbonate, and showed marked seasonal variation in alkalinity, Ca²⁺ content, Sr/Ca and Mg/Ca ratios. Although the variability in the water chemistry was relatively low (~10% relative standard deviation over the entire period), the trace-element contents in the ostracod shells tracked the seasonal change in the water chemistry of Maïques pool. Moreover, due to the rapid renewal of H. intermedia population, this species is able torecord in its shells the evolution of the water chemistry at a monthly time scale. Our results also showed that, in the Maïques pool system, ostracod Sr/Ca and Mg/Ca ratios increased with the decrease in water salinity.To our knowledge, this is the first geochemical study of ostracods dwelling in spring environments. The results of this study may be applied to paleohydrological reconstruction using ostracods preserved in sediments deposited around springs (i.e. travertine and tufa deposits).     

High precision glacial–interglacial benthic foraminiferal Sr/Ca records from the eastern equatorial Atlantic Ocean and Caribbean Sea

Glacial–interglacial variation in the marine Sr/Ca ratio has important implications for coral Sr thermometry [J.W. Beck et al., Science 257 (1992) 644–647]. A possible variation of 1–3% was proposed based on ocean models [H.M. Stoll and D.P. Schrag, Geochim. Cosmochim. Acta 62 (1998) 1107–1118]. Subsequently, studies have used fossil foraminifera to test this prediction [P.A. Martin et al., Geochem. Geophys. Geosyst. 1 (1999); H.M. Stoll et al., Geochim. Cosmochim. Acta 63 (1999) 3535–3547; H. Elderfield et al., Geochem. Geophys. Geosyst. 1 (2000)]. But whether some component of foraminiferal Sr/Ca variation can be uniquely ascribed to seawater Sr variation is still not clear. To address this question, we developed cleaning and analysis techniques and measured Sr/Ca ratios on individual shells of the modern benthic foraminifer Cibicidoides wuellerstorfi. We showed that different size shells have different Sr/Ca ratios; however, samples with shell sizes of 355–500 μm appear to have normally distributed Sr/Ca ratios (1σ=1.8%). For multi-shell measurements (with estimated errors of 0.12–0.39%), the ratio varied by as much as 7.2±0.5% during the last glaciation for two Caribbean records at the same site and by 3.7±0.5% over the past 40,000 yr for one record from the Sierra Leone Rise in the eastern equatorial Atlantic. The two Caribbean records are very similar indicating that the behavior of shell Sr uptake was identical locally and that the shell Sr/Ca ratio faithfully reflects the local environment. The Atlantic record differs from the Caribbean records by as much as several percent. Thus, the foraminiferal Sr/Ca changes cannot be solely due to changes in seawater Sr/Ca unless the glacial deep ocean had spatial variation in Sr/Ca well in excess of the modern ocean. Certain similarities between the three records do exist. Notably, the rate of change of Sr/Ca is similar between 9 and 0 ka (−0.25%/kyr) and between 25 and 16 ka (+0.16%/kyr). This suggests that during these intervals, benthic foraminiferal Sr/Ca was affected by similar large-scale variables. One of these variables may be the average marine Sr/Ca ratio; however, comparison with model predictions [H.M. Stoll and D.P. Schrag, Geochim. Cosmochim. Acta 62 (1998) 1107–1118] suggests other factors must also be considered. The discrepancies between the two sites may be related to the different water mass histories for the Caribbean and eastern Atlantic. Our results suggest that variation of the seawater Sr budget only partially contributed to C. wuellerstorfi Sr/Ca records, while other significant factors still need to be quantified. At present we cannot confidently determine past seawater Sr/Ca variation from our foraminiferal records.     

Calcium isotope fractionation in coccoliths of cultured Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa

Four species of marine calcifying algae, the coccolithophores Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 °C, and one species, C. leptoporus, under varying [CO₃²⁻], ranging from 105 to 219 μmol/kg. Calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e.g. Emiliania huxleyi (coccolithophores) and Orbulina universa (planktonic foraminifera) as well as inorganically precipitated CaCO₃, but also reveal small species specific differences. In contrast to inorganically precipitated calcite, but similar to E. huxleyi and O. universa, the carbonate ion concentration of the medium has no statistically significant influence on the Ca isotope fractionation of C. leptoporus coccoliths; however, combined data of E. huxleyi and C. leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium. Since coccoliths constitute a significant portion of the global oceanic CaCO₃ export production, the Ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the Ca sink of the ocean, one of the key parameters for modelling changes to the marine Ca budget over time. For the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic Ca sink (Δ_sed) of about − 1.3‰, but the observed inter- and intra-species differences point to possible changes in Δ_sed through earth history, due to changing physico-chemical conditions of the ocean and shifts in floral and faunal assemblages.     

Sea surface temperature and salinity reconstruction based on stable isotopes and Mg/Ca of planktonic foraminifera in the western Pacific Warm Pool during the last 155 ka

Changes in sea surface temperature(SST), seawater oxygen isotope(δ 18 O sw), and local salinity proxy(δ 18 O sw-ss) in the past 155 ka were studied using a sediment core(MD06-3052) from the northern edge of the western Pacifi c Warm Pool(WPWP), within the fl ow path of the bifurcation of the North Equatorial Current. Our records reveal a lead-lag relationship between paired Mg/Ca-SST and δ 18 O during Termination II and the last interglacial period. Similarity in SST between our site and the Antarctic temperature proxy and in CO 2 profi le showed a close connection between the WPWP and the Antarctic. Values of δ 18 O sw exhibited very similar variations to those of mean ocean δ 18 O sw, owing to the past sea-level changes on glacial-interglacial timescale. Calculated values of δ 18 O sw-ss refl ect a more saline condition during high local summer insolation(SI) periods. Such correspondence between δ 18 O sw-ss and local SI in the WPWP may refl ect complex interaction between ENSO and monsoon, which was stimulated by changes in solar irradiance and their infl uence on the local hydrologic cycle. This then caused a striking reorganization of atmospheric circulation over the WPWP.     

洞穴滴水、石笋中元素及元素比值对气候环境变化响应的研究进展

滴水/石笋元素是除δ18O和δ13C,研究气候环境变化的又一重要代用指标。外界气候环境变化通过改变表层岩溶带和岩溶含水层中的水文环境,甚至洞穴环境,进而影响元素的溶解、运移和沉淀过程,从而使得滴水/石笋中元素表现一定的变化规律。本文通过分析影响洞穴滴水元素及元素比值变化的因素：元素来源、水—岩相互作用和滞留时间、差异性淋滤、先期碳酸盐沉淀及分配系数的基础上,从元素对岩溶区“二元结构”和极端天气/气候事件响应的角度,探讨了滴水/石笋中元素的气候环境指示意义。取得了以下认识：① 强降水带来的冲刷作用和溶解作用,促进土壤和基岩中元素、胶体和天然有机质（NOM：Natural Organic Matter）等物质在短时间内快速溶解和运移,使滴水中元素含量增加;但随着降水增多带来的稀释作用,使得滴水/石笋中Mg,Sr和Ba等元素含量降低,因此,单一元素的解译较为复杂;② 基岩/溶液中元素溶解和沉积的差异,导致元素相对含量的变化,使得元素X/Ca值对外界环境的响应具有一致性,尤其是Mg/Ca和Sr/Ca值：在干旱条件下,降水减少导致方解石先期沉积（PCP：Prior Calcite precipitation）作用增强,使Mg/Ca和Sr/Ca值增大。但目前存在着一些问题：① Mg/Ca和Sr/Ca值变化对强降水事件的响应并不明显,可能与新、老水混合及元素溶解过程中的溶解比例差别不大有关;② 多源、多期混合水源会导致洞穴滴水元素对极端事件响应减弱;③ Mg/Ca和Sr/Ca的变化为解释δ18O的“雨量效应”及“源效应”提供了见解,但元素变化能否反映季风强度的变化,仍有待进一步的研究。基于以上认识,笔者提出开展更加系统的大气—土壤—包气带—洞穴的监测;开展更高分辨率、更长时间尺度的洞穴监测;开展多区域、多洞穴系统对比研究来更加深入地开展洞穴石笋元素研究。     

苏北盆地建湖隆起碳酸盐岩储层中的硫酸盐型热矿水成因

碳酸盐岩储层中的硫酸盐型热矿水是宝贵的旅游疗养资源。我国苏北盆地北部分布有丰富的热矿水,其中,盱眙县的一口热水井的单井流量达到3 616t·d-1,矿化度(TDS)达到4g·L-1,温度为53.5℃,为优质硫酸盐型热矿水。采用水化学和同位素方法,结合钻孔地质资料,研究了其形成机理。该地区热矿水的SO2-4离子含量较高,部分热矿水的阴离子中SO2-4离子占主导,成为硫酸盐型水。热水的氢氧稳定同位素(δ2 H、δ18 O)值证明了其来源于大气降水。建湖隆起存在石膏层,主要分布在白垩系浦口组,该组属盐湖相沉积,发育大范围的含膏质泥岩,其中石膏、硬石膏含量较多。根据水样的Sr/Ca摩尔比,该区热水中的硫酸盐来源于石膏的溶解。基于碳酸盐岩热水的pH值和SI值、14 C含量等数据的分析,排除了硫酸盐型热矿水的形成与金属矿的风化或氧化的关系,认为是石膏或硬石膏溶解形成。     

The (Na–Ca)amphibole–albite–chlorite–epidote–quartz geothermobarometer in the system S–A–F–M–C–N–H2O. 1. An empirical calibration

The proposed geothermobarometer is based on an empirical calibration which takes account of two equilibria involving the tremolite, edenite, pargasite and hastingsite components in amphiboles. It has applications to assemblages found in metabasic rocks of widely different chemical compositions (magnesian to Fe-rich metabasalts), and for metamorphism ranging from lower greenschist to highest amphibolite facies. Knowing the Si_(T1), Al^iv, Al^vi, Fe³⁺, Fe²⁺, Mg, Ca, Na_M4, Na_A and A vacancy in an amphibole, and the Al³⁺ and X _Mg in coexisting epidote and chlorite, it is possible to calculate two values of In K _d for this assemblage. These equilibria involve edenite-tremolite and (pargasite/hastingsite)-tremolite end-members in amphibole (the calculation program is given). For these equilibria, the isopleths (iso-values of K _d) have been calculated for 0.27 < X _Mg < 0.75 and 0 < X _Fe3+= Fe³⁺/(Fe³⁺+ Al^vi) < 0.8. It is then possible to determine pressure and temperature directly when X _Mg, X _Fe3+, In K _d for tremoliteedenite and In K _d for (pargasite/hastingsite)-tremolite are known. Application of this geothermobarometer is limited to Ca-free plagioclase assemblages, and complete P–T paths can be drawn only if all the minerals are considered together. Phase relations at successive stages of crystallization can be constrained by studying the relationships between the coexisting minerals, their zoning and the metamorphic fabrics.     

Geochemistry of coral from Papua New Guinea as a proxy for ENSO ocean–atmosphere interactions in the Pacific Warm Pool

A Porites sp. coral growing offshore from the Sepik and Ramu Rivers in equatorial northern Papua New Guinea has yielded an accurate 20-year history (1977–1996) of sea surface temperature (SST), river discharge, and wind-induced mixing of the upper water column. Depressions in average SSTs of about 0.5–1.0 °C (indicated by coral Sr/Ca) and markedly diminished freshwater runoff to the coastal ocean (indicated by coral δ¹⁸O, δ¹³C and UV fluorescence) are evident during the El Niño – Southern Oscillation (ENSO) events of 1982–1983, 1987 and 1991-1993. The perturbations recorded by the coral are in good agreement with changes in instrumental SST and river discharge/precipitation records, which are known to be diagnostic of the response of the Pacific Warm Pool ocean–atmosphere system to El Niño. Consideration of coastal ocean dynamics indicates that the establishment of northwest monsoon winds promotes mixing of near-surface waters to greater depths in the first quarter of most years, making the coral record sensitive to changes in the Asian–Australian monsoon cycle. Sudden cooling of SSTs by 1°C following westerly wind episodes, as indicated by the coral Sr/Ca, is consistent with greater mixing in the upper water column at these times. Furthermore, the coral UV fluorescence and oxygen isotope data indicate minimal contribution of river runoff to surface ocean waters at the beginning of most years, during the time of maximum discharge. This abrupt shift in flood-plume behaviour appears to reflect the duration and magnitude of northwest monsoon winds, which tend to disperse flood plume waters to a greater extent in the water column when wind-mixing is enhanced. Our results suggest that a multi-proxy geochemical approach to the production of long coral records should provide comprehensive reconstructions of tropical paleoclimate processes operating on interannual timescales.