海洋钙离子非保守行为及海洋钙问题

钙离子是海洋11种常量离子之一,与钠、钾等离子的保守性不同,钙离子在海洋中的分布表现出微小但系统的变化。钙离子的变化往往与海洋碳酸钙的形成和溶解过程有关,所以,钙离子可直接指示海洋碳酸钙通量（深层海洋碳通量的主要组成部分）。同时,碳酸钙沉淀或溶解又会改变总碱度和溶解无机碳,通过钙离子变化也能间接探讨海洋碳酸盐系统和海洋吸收CO2的能力。介绍了以碳酸钙溶解形成超额钙为主的海洋钙离子多种非保守行为及其控制过程,讨论这些过程对海水组成和海洋碳酸盐系统的影响,探讨未来海洋酸化条件下钙离子可能的变化及其潜在的效应,最后展望在南海开展钙离子精细行为的研究意义。      

影响C4草本植物C/N比值变化的因素与土壤有机C积累的关系

文章对采自贵州从低海拔的东部到高海拔的西部且大致平行的石灰岩和砂岩两地带均生长的3种C₄草本植物,即巴茅(Miscanthusfloridulus)、白茅(Imperatacylindrica)和类芦(Neyraudiareynaudiana),以及相对应的土壤表层样品,进行了营养元素和C同位素组成分析;研究营养元素含量随着海拔的不同而出现的变化趋势,以及这些元素之间的相互协变作用,尤其是Ca和N之间的相互协变作用对植物的N含量、C/N比值和^δ13C值的影响,以了解植物的C/N比值(指示植物残留物质量的一种标志)与土壤有机C积累的关系。研究结果表明,植物的N含量和^δ13C值具有随海拔的上升而显著增大趋势,而植物的C/N比值在砂岩地区虽有减小的趋势,在石灰岩地带则没有。对所研究的C4草本植物来说,在土壤pH值为5.8的中性条件下显示出Ca的最大吸收,因此,Ca与其他营养元素之间的协变模式在两种土壤类型中表现出相反的倾向,并存在土壤交换性Ca的边界浓度:当土壤可交换性Ca的含量为2.24mg/g,相应土壤的pH值在5.8以下时,随着土壤可交换性Ca浓度的增大,植物的N含量上升,而植物的C/N比值会显著降低;当Ca在边界浓度以上时,随着土壤可交换性Ca浓度的增大,植物的N含量下降,而植物的C/N比值有增加的趋势。由此可见,植物残留物的N含量和C/N比值受Ca元素含量的相     

Inverse modelling using PS‐InSAR data for improved land subsidence simulation in Las Vegas Valley,Nevada

Las Vegas Valley has had a long history of groundwater development and subsequent surface deformation. InSAR interferograms have revealed detailed and complex spatial patterns of subsidence in the Las Vegas Valley area that do not coincide with major pumping regions. This research represents the first effort to use high spatial and temporal resolution subsidence observations from InSAR and hydraulic head data to inversely calibrate transmissivities (T), elastic and inelastic skeletal storage coefficients (S_ke and S_kv) of the developed‐zone aquifer and conductance (CR) of the basin‐fill faults for the entire Las Vegas basin. The results indicate that the subsidence observations from InSAR are extremely beneficial for accurately quantifying hydraulic parameters, and the model calibration results are far more accurate than when using only groundwater levels as observations, and just a limited number of subsidence observations. The discrepancy between distributions of pumping and greatest levels of subsidence is found to be attributed to spatial variations in clay thickness. The Eglington fault separates thicker interbeds to the northwest from thinner interbeds to the southeast and the fault may act as a groundwater‐flow barrier and/or subsidence boundary, although the influence of the groundwater barrier to this area is found to be insignificant. Copyright © 2016 John Wiley & Sons, Ltd.     

Origin and evolution of geothermal fluids from Las Tres Vírgenes and Cerro Prieto fields,Mexico – Co-genetic volcanic activity and paleoclimatic constraints

Major and trace elements, noble gases, and stable (δD, δ¹⁸O) and cosmogenic (³H, ¹⁴C) isotopes were measured from geothermal fluids in two adjacent geothermal areas in NW-Mexico, Las Tres Vírgenes (LTV) and Cerro Prieto (CP). The goal is to trace the origin of reservoir fluids and to place paleoclimate and structural-volcanic constraints in the region. Measured ³He/⁴He (R) ratios normalized to the atmospheric value (R_a = 1.386 × 10⁻⁶) vary between 2.73 and 4.77 and are compatible with mixing between a mantle component varying between 42 and 77% of mantle helium and a crustal, radiogenic He component with contributions varying between 23% and 58%. Apparent U–Th/⁴He ages for CP fluids (0.7–7 Ma) suggest the presence of a sustained ⁴He flux from a granitic basement or from mixing with connate brines, deposited during the Colorado River delta formation (1.5–3 Ma). Radiogenic in situ ⁴He production age modeling at LTV, combined with the presence of radiogenic carbon (1.89 ± 0.11 pmC – 35.61 ± 0.28 pmC) and the absence of tritium strongly suggest the Quaternary infiltration of meteoric water into the LTV geothermal reservoir, ranging between 4 and 31 ka BP. The present geochemical heterogeneity of LTV fluids can be reconstructed by mixing Late Pleistocene – Early Holocene meteoric water (58–75%) with a fossil seawater component (25–42%), as evidenced by Br/Cl and stable isotope trends. CP geothermal water is composed of infiltrated Colorado River water with a minor impact by halite dissolution, whereas a vapor-dominated sample is composed of Colorado River water and vapor from deeper levels. δD values for the LTV meteoric end-member, which are 20‰–44‰ depleted with respect to present-day precipitation, as well as calculated annual paleotemperatures 6.9–13.6 °C lower than present average temperatures in Baja California point to the presence of humid and cooler climatic conditions in the Baja California peninsula during the final stage of the Last Glacial Pluvial period. Quaternary recharge of the LTV geothermal reservoir is related to elevated precipitation rates during cooler-humid climate intervals in the Late Pleistocene and Early Holocene. The probable replacement of connate water or pore fluids by infiltrating surface water might have been triggered by enhanced fracture and fault permeability through contemporaneous tectonic–volcanic activity in the Las Tres Vírgenes region. Fast hydrothermal alteration processes caused a secondary, positive δ¹⁸O-shift from 4‰ to 6‰ for LTV and from 2‰ to 4‰ for CP geothermal fluids since the Late Glacial infiltration.     

二连盆地与地沥青密切相关的砂岩型铀矿床微观矿物特征及成因分析

内蒙古二连盆地产在下白垩统碎屑岩系中的砂岩型铀矿床,其矿化与地沥青密切相关,有铀矿物存在之处必有地沥青;岩石中也普遍含地沥青。笔者通过蚀刻α径迹示踪,对铀含量在(200~1770)×10~(-6)的碎屑岩进行扫描电镜分析,采用分子量计算方法确定了该地区含铀碎屑岩中的铀是以多种超显微铀矿物形式存在。其中,以赛汉高毕铀矿床为代表,铀主要形成复成分磷钙铀矿。其它铀矿床也普遍有复成分磷钙铀矿产出:巴彦乌拉矿床样品因钙含量低、硅含量高,则铀石多于复成分磷钙铀矿;道尔苏矿床以铀石和磷铀矿为主,有少量沥青铀矿及复成分磷钙铀矿;哈达图矿床主要是沥青铀矿,未见复成分磷钙铀矿。除了地沥青之外,各矿床中与铀矿物共生的主要矿物还有草莓状、鲕粒状黄铁矿。由此推断,铀矿床的可能成因是:来自盆地深部的UH_3、PH_3、CaH_2、SiH_4、FeH_2、H_2S等在伴随油气向上运移过程中,由于温度、压力降低和氧化作用而发生分解及凝聚,形成草莓状、鲕粒状黄铁矿;同时派生出含U、P、Si、Ca等的氧化物的低温热水溶液,并最终结晶析出铀矿物,形成有大量黄铁矿共生的铀矿体;而油气经过长期挥发,最终演变成地沥青,成为铀矿物的载体。     

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.     

近800a来内蒙古岱海湖水的盐度定量及其气候意义

在干旱半干旱地区 ,封闭湖泊的湖水盐度对气候变化反应敏感。首先通过现生介形类 (Lim nocytherecf.inopinata)壳体与湖水Sr/Ca比值的测定确定了Sr/Ca的分配系数 ;然后测试现代岱海湖水盐度与湖水Sr/Ca比值 ,建立湖水盐度与湖水Sr/Ca比值的函数关系 ;最后利用湖泊沉积剖面中介形类壳体的Sr/Ca比值定量恢复了岱海湖水近 80 0a来的盐度。通过分析岱海湖水盐度变化过程 ,揭示了研究区小冰期前期降水增加的冷湿气候 ,这明显不同于东部其它地区的冷干气候 ;研究区在小冰期中后期以偏干旱气候为主 ,这与东部其它地区干冷气候相一致 ;推测了 2 1世纪初 10～ 2 0a ,岱海地区降水将有所增加 ,干旱趋于缓和。     

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.