Chemical and isotopic assessment of surface water–shallow groundwater interaction in the arid Grande river basin,North-Central Chile

ABSTRACT

This paper analyses the composition of surface water and shallow groundwater in the Grande River basin, North-Central Chile, using this information to characterize water interactions. Chemical and isotopic data for surface water and groundwater (7 and 6 sampling locations, respectively) were obtained from three sampling campaigns performed in March–April (autumn), August–September (late winter) and December (early summer) 2012. Precipitation samples were also collected. Data was processed using spatial distribution charts, Piper and Stiff diagrams, and multivariate analysis. In general, the results for each method converge on a high degree of connectivity between surface water and shallow groundwater in the study area. Furthermore, approximately a 10% of groundwater contribution to the surface flow discharge was estimated for a particular reach. This multi-method approach was useful for the characterization of surface water–groundwater interactions in the Grande River basin, and may become a suitable and replicable scheme for studies in arid and semi-arid basins facing similar water management challenges.

Editor D. Koutsoyiannis; Associate editor B. Dewals     

Analyzing Effects of Shrub Canopy on Throughfall and Phreatic Water Using Water Isotopes,Western China

Alpine shrub Quercus aquifolioides was selected to study the effects of shrub canopy on throughfall and phreatic water by analyzing the isotopic time series of precipitation, canopy throughfall and phreatic water and examining correlations among these series in Wolong Nature Reserve, Western China. Based on analysis of precipitation data in 2003, the local meteoric water line during the rainy season was δD = 8.28 × δ¹⁸O + 8.93, and the primary precipitation moisture in this region originated from the Pacific Ocean in the summer. Stable isotope analysis showed that the main supply of throughfall and phreatic water was from precipitation, and the shrub canopy has an important effect on the processes of rainwater transmuted into throughfall and phreatic water. Moreover, the differences of δD and δ¹⁸O values between rainwater and throughfall were relevant to rainfall. Due to interception of the shrub canopy, there had a response hysteresis of phreatic water to the various rainfall events, which was mostly 2 days, except that this hysteresis was ≤1 day when rainfall was >15 mm/day.     

Equilibrium thallium isotope fractionation and its constraint on Earth’s late veneer

Equilibrium isotope fractionation of thallium(Tl) includes the traditional mass-dependent isotope fractionation effect and the nuclear volume effect(NVE). The NVE dominates the overall isotope fractionation, especially at high temperatures. Heavy Tl isotopes tend to be enriched in oxidized Tl^3+-bearing species. Our NVE fractionation results of oxidizing Tl^+ to Tl^3+ can explain the positive enrichments observed in ferromanganese sediments. Experimental results indicate that there could be0.2–0.3 e-unit fractionation between sulfides and silicates at 1650 ℃. It is consistent with our calculation results,which are in the range of 0.17–0.38 e-unit. Importantly,Tl’s concentration in the bulk silicate Earth(BSE) can be used to constrain the amount of materials delivered to Earth during the late veneer accretion stage. Because the Tl concentration in BSE is very low and its Tl isotope composition is similar with that of chondrites, suggesting either no Tl isotope fractionation occurred during numerous evaporation events, or the Tl in current BSE was totally delivered by late veneer. If it is the latter, the Tl-contentbased estimation could challenge the magnitude of late veneer which had been constrained by the amount of highly siderophile elements in BSE. Our results show that the lateaccreted mass is at least five-times larger than the previously suggested magnitude, i.e., 0.5 wt% of current Earth’s mass. The slightly lighter 205 Tl composition of BSE relative to chondrites is probable a sign of occurrence of Tlbearing sulfides, which probably were removed from the mantle in the last accretion stage of the Earth.     

Late Quaternary tephrostratigraphy and pollen stratigraphy of Uwa Formation,Shikoku Island,SW Japan: Reconsidering the MIS 11 super-interglacial horizon

We investigated a late Quaternary terrestrial sedimentary sequence (Uwa Formation) in core IC2, from a site adjacent to that of the reported core IC on NW Shikoku Island, SW Japan, and developed its tephra and pollen stratigraphy to refine the age model of the formation. First, we identified 19 horizons with high glass shard concentrations in the IC2 core sediments as possible tephras or cryptotephras, and correlated them with reported tephras on the basis of the major- and trace-element compositions of their glass shards. All correlated widespread tephras and cryptotephras were products of volcanoes in the Kyushu volcanic zone (Aso, Kakuto, Aira, Ata, and Kikai calderas). Second, we confirmed the presence in core IC2 of two pollen zones dominated by Quercus subgen. Cyclobalanopsis, which is an indicator of very warm interglacial vegetation. In the Japanese Islands, these two vegetation zones have usually been considered to characterize marine isotopic stages (MISs) 1 and 11. A previous study of the Uwa Formation correlated the upper pollen zone to MIS 1, but the lower zone was not correlated to MIS 11; rather, it was inferred to be older than MIS 12 because it was stratigraphically below the “Oda” tephra (equivalent to a distal Kasamori 5 [Ks5] tephra [MIS 12]). In this study, however, noting that the Naruohama-IV tephra (Nh-IV; MIS 10d) and Ks5 cannot be distinguished by their shard chemistries, we inferred that the suggested “Oda” tephra actually correlates to Nh-IV, rather than to the Ks5 tephra. By re-assigning the “Oda” tephra to Nh-IV, we could correlate the underlying Quercus subgen. Cyclobalanopsis-abundant zone to MIS 11 and, consequently, a pair of pollen zones indicating cool and warm conditions below the MIS 11 pollen zone to MISs 12 and 13, respectively. The resulting age model whereby tephra and pollen constraints are integrated showed a roughly constant sedimentation rate from MIS 13, without any long-term gaps; further, our MIS 13 horizon in core IC2 corresponds to the reported 1 Ma tephra horizon in core IC. Therefore, these findings represent a dramatic change in the Uwa Formation age model and validate the Uwa Formation as one of the most useful terrestrial archives of Quaternary tephrostratigraphy and paleoclimatic fluctuation in SW Japan.     

辽宁小佟家堡子金矿床成矿流体特征及来源讨论

小佟家堡子金矿床地处辽宁青城子矿田东南部,为一大型蚀变岩型矿床。矿床产于辽河群大石桥组三段白云石大理岩中,矿体呈层状、似层状产出。矿床由热液叠加改造作用形成,历经石英-黄铁矿、石英-碳酸盐两个阶段。流体包裹体研究表明,该矿床成矿流体属中低温、低盐Na Cl-H2O型体系热液。碳氢氧同位素地球化学的研究表明,石英-黄铁矿阶段成矿流体氧同位素δ18O组成在15.2‰~18.4‰,碳同位素δ13CV-PDB组成在-7.4‰~-13.2‰,氢同位素δD组成为-89.3‰~-92.2‰,反应该阶段成矿流体主要来自岩浆水并伴有少量的大气降水。石英-碳酸盐阶段成矿流体氧同位素δ18O组成在17‰~17.8‰,碳同位素δ13CV-PDB组成在-12.3‰~-13.5‰,氢同位素组成δD为-87.7‰~-90.4‰,表明该阶段成矿流体主要来自大气降水。     

Long-Term Observations of Isotope Ratio Accuracy and Reproducibility Using Quadrupole ICP-MS

High precision isotope ratio and trace element determination can be achieved with modern quadrupole ICP-MS provided that short and long-term instrument performance is accurately monitored. Here we present results for the isotope ratios ⁶Li/⁷Li, ¹⁴⁷Sm/¹⁴⁹Sm, ¹⁶⁰Dy/¹⁶¹Dy, ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb and ²³⁵U/²³⁸U with which we determined long-term isotope ratio stability of relevance to both trace element and isotope determination. With respect to trace element determination, we first present long-term observations regarding oxide formation rates of Ba and Nd on light REE and heavy REE, as well as Zr on Ag. These showed good correlations and could be used to correct effectively the interference. The efficacy of this correction was demonstrated with analyses of the rock reference material BHVO-2 at both low and high oxide formation rates. Next, we studied the long-term reproducibility of a Dy isotope ratio that was measured to correct for the isobaric interference on Gd. It was found that, regardless of tuning condition, the ratio reproduced very well (0.58% RSD, 1s) and that the estimate of the Gd concentration did not suffer from the large correction (> 10%) caused by the Dy isobar. Long-term reproducibilities of Li, Sm and U isotope ratios, required for accurate mass bias correction when isotopically enriched internal standards of these elements are employed, were measured in the rock reference materials AGV-2 and JA-3 over a time period of up to 3 years. As expected, the Li isotope ratio showed the largest variability (RSD = 7%), but the other two ratios had relative external reproducibilities of only 1.01% (1s, U) and 0.67% (Sm). The mass bias-induced scatter in measurements for Sm and U was so small that the internal standard correction was effective, even for samples with high concentrations of these elements. With regard to Pb-isotope ratio determination, we also present long-term reproducibility for NIST SRM 982, run as an unknown and two accuracy tests for Pb separated from granitoids and from meteorites. It is demonstrated that the obtained ratios, including those involving ²⁰⁴Pb, are accurate relative to MC-ICP-MS determinations and of comparable precision to conventional TIMS analysis. The excellent agreement between all data sets shows the potential of modern quadrupole ICP-MS instrumentation for Pb-isotope determination, particularly for samples with very low Pb content.     

Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

广西钦州湾百年来红树林演变的有机碳同位素和孢粉示踪及其影响因素

气候变化和人类活动制约下的红树林演变是一种长时间尺度效应,而沉积物则是记录这种响应的最佳档案。采用古生态学研究思路,选择有效的示踪参数是解读这一档案的有效途径。本文通过广西钦州湾红树林区1根柱状沉积物中有机碳同位素(δ13C)、C/N分析和孢粉鉴定,以沉积物中的红树林源有机碳贡献和红树植物孢粉组合为示踪参数,在210Pb年龄框架构建的基础上,通过对比研究红树林源有机碳贡献和红树孢粉组合特征,揭示百年来钦州湾红树林兴衰和群落演替规律;进而重塑其红树林演变历史:兴盛期(1864-1918年)、衰退期(1918-1968年)和低谷期(1968-2007年),这与土地替代、遥感分析和现场勘测数据较为吻合。结合气候变化和人类活动资料,发现钦州湾红树林的近期衰退主要源于人类活动的影响,尤其是虾塘围垦;而与气候变化关系不大。     

Diet of Haplognathia ruberrima (Gnathostomulida) in a Caribbean marine mangrove

Haplognathia ruberrima is a cosmopolitan gnathostomulid species found in sulfur bacterial mats in mangroves in Guadeloupe (French West Indies). Haplognathia ruberrima presents a δ¹³C value lower than all measured meiofaunal grazers and lower than the available measured food sources of this environment. This low δ¹³C value can not be due to specific ingestion of ¹³C‐depleted methanogenic bacteria because abundances of those bacteria are reduced in surficial and deep sediments as revealed by δ¹³C of bacterial fatty acid. According to scanning electron microscope observations, no bacterial ectosymbionts were observed at the surface of the gnathostomulids, and transmission electron microscope views revealed the absence of bacterial endosymbionts. Energy‐dispersive X‐ray spectroscopy analysis detected low levels of sulfur (0.32%±0.8) in biological tissues of H. ruberrima, confirming the absence of thioautotrophic bacterial symbionts in these animals. Consequently, the low δ¹³C value of H. ruberrima can not be due to the presence of sulfur‐oxidizing symbionts but more probably to the selective and exclusive consumption of free‐living, sulfur‐oxidizing bacteria.