A multi-isotope (δD, δO,Sr/Sr,and δB) approach for identifying saltwater intrusion and resolving groundwater evolution along the Western Caprock Escarpment of the Southern High Plains,New Mexico

Declining water levels in arid and semi-arid regions increase an aquifer’s vulnerability to natural and anthropogenic influences. A multi-isotope (δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B) approach was used to resolve the geochemical evolution of groundwater in a declining aquifer in a semi-arid region of the southwestern USA as groundwater composition reacts to source-water mixing, cross-formational flow including saltwater intrusion, water–rock interaction, and likely agricultural recharge. Sub-aquifers or local flow systems are present in the Southern High Plains aquifer along the Western Caprock Escarpment in New Mexico, and the study site’s local flow system contains a Na–Cl, high dissolved-solids groundwater that flows from the escarpment until it mixes with a high quality regional aquifer or regional flow system. The local flow system contains water that is similar in composition to the underlying, upper Dockum Group aquifer. Saltwater found in the upper Dockum Group aquifer likely originates in the adjacent Pecos River Basin and crosses beneath or possibly through the hydrologic divide of the Western Caprock Escarpment. Strontium concentrations of 0.9–31 mg/L and a ⁸⁷Sr/⁸⁶Sr range of 0.70845–0.70906 were sufficient to estimate source-water fractions, mixing patterns, and contributions from chemical weathering through mass balance inverse calculations. Boron concentrations (59–1740 mg/L) and δ¹¹B values (+6.0–+46.0‰) were used to confirm source-water mixing, further evaluate water–rock interaction, and examine the influence of possible agricultural recharge. Alteration of B concentrations and δ¹¹B values in an area of likely agricultural recharge indicated the loss of B and decrease in δ¹¹B values likely from plant uptake, adsorption, and weathering contributions in the soil/vadose zone prior to recharge. The effectiveness of ⁸⁷Sr/⁸⁶Sr and δ¹¹B for resolving the geochemical influences in groundwater in the Southern High Plains along the Western Caprock Escarpment allowed for the reinterpretation of the isotopic composition of water that has been shown to be highly variable in the Southern High Plains. This study shows the utility of a multi-isotope approach for resolving the geochemical evolution of groundwater in an aquifer that has a complex relationship with underlying aquifers and the applicability of these isotopes as indicators of the alteration of source waters from natural or anthropogenic influences.     

Patterns and implications of plant-soil δC and δN values in African savanna ecosystems

Southern African savannas are mixed plant communities where C₃ trees co-exist with C₄ grasses. Here foliar δ¹⁵N and δ¹³C were used as indicators of nitrogen uptake and of water use efficiency to investigate the effect of the rainfall regime on the use of nitrogen and water by herbaceous and woody plants in both dry and wet seasons. Foliar δ¹⁵N increased as aridity rose for both C₃ and C₄ plants for both seasons, although the magnitude of the increase was different for C₃ and C₄ plants and for two seasons. Soil δ¹⁵N also significantly increased with aridity. Foliar δ¹³C increased with aridity for C₃ plants in the wet season but not in the dry season, whereas in C₄ plants the relationship was more complex and non-linear. The consistently higher foliar δ¹⁵N for C₃ plants suggests that C₄ plants may be a superior competitor for nitrogen. The different foliar δ¹³C relationships with rainfall may indicate that the C₃ plants have an advantage when competing for water resources. The differences in water and nitrogen use likely collectively contribute to the tree-grass coexistence in savannas. Such differences facilitate interpretations of palaeo-vegetation composition variations and help predictions of vegetation composition changes under future climatic scenarios.     

K–Ar dating and δO–δD tracing of illitization within and outside the Shea Creek uranium prospect,Athabasca Basin,Canada

Isotope analyses (K–Ar, δ¹⁸O and δD) were performed on illite from both the sandstone cover and the underlying basement, close to and distant from Shea Creek, an unconformity-type U deposit (Athabasca Basin, Canada); the illite had previously been characterized crystallographically. In the barren areas away from deposit, illite is mainly of the cis-vacant 1M polytype occurring as relatively coarse-grained lath-shaped particles, while it occurs as fine-grained particles of the trans-vacant 1M type next to and in the U mineralized strata. The tectonic-induced hydrothermal system that favored illite crystallization was multi-episodic 1453 ± 2, 1330 ± 20 and probably about 1235 Ma ago. These illite-forming episodes appear to have occurred contemporaneously to those favoring the concentration of the associated U oxides, which were dated independently by the U–Pb method in the Shea Creek deposits and elsewhere in the Athabasca Basin.     

δB, Sr, Mg and B in a modern Porites coral: the relationship between calcification site pH and skeletal chemistry

Sr/Ca, B/Ca, Mg/Ca and δ¹¹B were determined at high spatial resolution across ∼1 year of a modern Hawaiian Porites lobata coral by secondary ion mass spectrometry (SIMS). We observe significant variations in B/Ca, Mg/Ca, Sr/Ca and δ¹¹B over short skeletal distances (nominally equivalent to periods of <20 days). This heterogeneity probably reflects variations in the composition of the extracellular calcifying fluid (ECF) from which the skeleton precipitates. Calcification site pH (total scale) was estimated from skeletal δ¹¹B and ranged from 8.3 to 8.8 (± ∼0.1) with a mean of ∼8.6. Sr/Ca and B/Ca heterogeneity is not simply correlated with calcification site pH, as might be expected if Ca-ATPase activity increases the pH and decreases the Sr/Ca and B(OH)₄⁻/CO₃²⁻ ratios of the ECF. We produced a simple model of the ECF composition and the skeleton deposited from it, over a range of calcium transport and carbonate scenarios, which can account for these observed geochemical variations. The relationship between the pH and Sr/Ca of the ECF is dependent on the concentration of DIC at the calcification site. At higher DIC concentrations the ECF has a high capacity to buffer the [H⁺] changes induced by Ca-ATPase pumping. Conversely, at low DIC concentrations, this buffering capacity is reduced and ECF pH changes more rapidly in response to Ca-ATPase pumping. The absence of a simple correlation between ECF pH and skeletal Sr/Ca implies that calcification occurred under a range of DIC concentrations, reflecting variations in the respiration and photosynthesis of the coral and symbiotic zooxanthellate in the overlying coral tissues. Our observations have important implications for the use of coral skeletons as indicators of palaeo-ocean pH.     

两种不同燧石中α-石英 β-石英相变的研究

 利用差热分析和高温 X-射线衍射分析的实验手段,对两种不同燧石的α-石英⇔β-石英的相变反应进行了研究。结果表明,它们在相变热效应和晶格参数随温度的变化规律等方面存在着明显的差异。这种差异性的存在是由于两者内部α-石英颗粒的粒度、双晶发育程度以及燧石本身的致密度不同所造成。     

Geochemistry,isotopic composition (δO, δH,Sr/Sr,Nd/Nd) in the groundwater of French Guiana as indicators of their origin,interrelations

The current use of untreated river water for drinking purposes by the population of French Guiana has important impacts on public health. Consequently, groundwater is of major importance as a possible alternative drinking water supply to reduce these impacts. Since French Guiana belongs to the Guyana Shield, sustainable water management can be expected to depend increasingly on water from fissured aquifers in hard rocks. Groundwater samples were collected from shallow drill holes in the densely populated coastal area, and deeper wells in the basement (around Cayenne and along the Maroni and Oyapock rivers). This study reports on major and trace elements for which Na⁺ and Ca²⁺ excess with regard to Cl reflect the role of water-rock interaction, as well as Sr and Nd isotopes that reflect the role of the different lithologies. δ¹⁸O and δD in waters give constraints on the water cycle (recharge and evaporation processes).     

两种不同燧石中α-石英 β-石英相变的研究

利用差热分析和高温 X-射线衍射分析的实验手段,对两种不同燧石的α-石英⇔β-石英的相变反应进行了研究。结果表明,它们在相变热效应和晶格参数随温度的变化规律等方面存在着明显的差异。这种差异性的存在是由于两者内部α-石英颗粒的粒度、双晶发育程度以及燧石本身的致密度不同所造成。     

Hydrological budget,carbon sources and biogeochemical processes in Lac Pavin (France): Constraints from δO of water and δC of dissolved inorganic carbon

Lac Pavin (French Massif Central) is a permanently stratified lake: the upper water layers (mixolimnion, from 0 to 60 m depth) are affected by seasonal overturns, whereas the bottom water layers (monimolimnion, from 60 to 90 m depth) remain isolated and are never mixed. Hence, they are capable of storing important quantities of dissolved gases, mainly CO₂. With the aim of better constraining the water balance and of gaining new insights into the carbon cycle of Lac Pavin, an isotopic approach is used. The δ¹⁸OH₂O$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}$ profiles lead the authors to give a new evaluation of the evaporation flow rate (8 L s⁻¹), and to propose and characterize two sub-surface springs. The sub-surface spring located at the bottom of the lake can be deduced from the 1% isotopic difference between the upper water layers (mean δ¹⁸OH₂O$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}$ value: −7.3‰) and the bottom water layers (δ¹⁸OH₂O=-8.4‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}=-8.4‰$). It is argued that this sub-surface spring has isotopic and chemical characteristics similar to those of the magmatic CO₂-rich spring (i.e. Fontaine Goyon, δ¹⁸OH₂O=-9.4‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}=-9.4‰$), and we calculate its flow rate of 1.6 L s⁻¹. The second sub-surface spring is located around 45 m depth, with a composition close to those of the water surface streams (δ¹⁸OH₂O<-7.6‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}<-7.6‰$).     

低δ18O岩浆岩的成因

具有显著低于正常幔源岩浆δ¹⁸O值的岩浆岩是地球上比较罕见的一种岩石,其形成需要特殊的岩浆过程。虽然岩浆分异过程基本上不改变氧同位素组成,但水岩反应可以明显改变岩石的氧同位素组成,高温水岩反应会导致岩石的氧同位素组成显著降低,这得到了理论计算的支持。对黄石高原流纹岩和冰岛玄武岩这两个典型的低δ¹⁸O岩浆实例的长期研究发现, 在地表遭受了高温热液蚀变的低δ¹⁸O岩石部分熔融或者被岩浆同化是形成低δ¹⁸O岩浆的重要机制,这通常通过裂谷构造带破火山口的垮塌来实现。塞舌尔和碾子山代表了结晶于低δ¹⁸O岩浆的花岗岩实例,其形成需要源区有亏损¹⁸O的地壳物质参与。大别-苏鲁造山带超高压变质岩亏损¹⁸O的幅度和这些亏损¹⁸O岩石的分布面积都非常令人瞩目。对这些超高压变质岩的原岩进行氧同位素研究,能够为其这些低δ¹⁸O岩石的成因提供有力的制约。目前已经在北淮阳花岗岩中报道了具有新元古代年龄和低δ¹⁸O 值的锆石。研究显示,这些花岗岩可能经历了两次高温水岩反应,第一次导致了低¹⁸O岩浆的形成和低δ¹⁸O值锆石的结晶,第二次则进一步降低了其它矿物的δ¹⁸O值,导致了氧同位素不平衡。对这些低δ¹⁸O花岗岩的深入研究,特别是进行原位微区分析,不仅有助于我们深入认识低δ¹⁸O岩浆的形成机理,而且有助于进一步理解水岩反应中元素和同位素的地球化学行为。     

Rb‐Sr geochronology and Sr isotopic composition of Devonian granitoids,eastern Tasmania

Biotite igneous ages and well‐defined isochron ages of plutons from the composite Blue Tier Batholith and the Coles Bay area in northeastern Tasmania range from 395 to 370 Ma. The older limit of this range, for the George River granodiorite, is considerably older than any age previously recorded for NE Tasmania. The ages of the youngest plutons (Mt Paris and Anchor granites), which host cassiterite ores, record pervasive hydrothermal alteration events. The initial ⁸⁷Sr/⁸⁰Sr ratios of the granitoids range from 0.7061 to 0.7136 and suggest different protolith compositions, consistent with mineralogical and geochemical characteristics of each pluton. The S‐type garnetbiotite granites (Ansons Bay and Booby alia granites) have initial ratios greater than 0.7119, indicative of enriched, high Rb/Sr ratio, crustal source‐rocks of Proterozoic age (1700–800 Ma). The S‐type biotite granites (Poimena and Pearson granites) have relatively high initial ⁸⁷Sr/⁸⁶Sr ratios (0.7070, 0.7105) but overlap with those of the I‐type granodiorites (George River, Scamander Tier, Pyengana and Coles Bay granodiorites) which are in the range of 0.7061 to 0.7073. The initial ratios of the enriched altered plutons are poorly constrained, and on both hand‐specimen and thin‐section scales, reveal open‐system Sr isotopic patterns.

Isochron ages for the arenite‐lutite and lutite sedimentary associations of the Mathinna Beds, which are intruded by the granitoids, reflect an approach to Sr isotopic equilibrium during regional metamorphism. The metamorphic age (401 ± 7 Ma) of the early Pragian arenite‐lutite association indicates a relatively small time interval between deposition, regional metamorphism and granitoid intrusion. The isotopic age for the lutite sedimentary association (423 ± 22 Ma) is tentatively correlated with a Benambran‐age burial metamorphic event that has not previously been recorded in Tasmania.     

Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

Origin and migration of brines from Paleozoic strata in Central Tarim,China: constraints from 87Sr/86Sr, δD, δ18O and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, and δ¹⁸O of oilfield waters, and ⁸⁷Sr/⁸⁶Sr of whole rock were measured from Paleozoic strata in the Central Tarim basin, NW China. The aim is to elucidate the origin and migration of formation water and its relation to petroleum migration. High salinity oilfield waters in Carboniferous, Silurian and Ordovician reservoirs have maintained the same Na/Cl ratio as seawater, indicative of subaerially evaporated seawater. Two possible sources of evaporitic water are Carboniferous (C_II) and Cambrian, both of which contain evaporitic sediments. Geographic and stratigraphic trends in water chemistry suggest that most of the high salinity water is from the Cambrian. Strontium, H and O isotopes as well as ion chemistry indicate at least 3 end member waters in the basin. High-salinity Cambrian evaporitic water was expelled upward into Ordovician, Silurian and Carboniferous reservoirs along faults and fractures during compaction and burial. Meteoric water has likely invaded the section throughout its history as uplift created subaerial unconformities. Meteoric water certainly infiltrated Silurian and older strata during development of the C_III unconformity and again in recent times. Modern meteoric water enters Carboniferous strata from the west and flows eastward, mixing with the high salinity Cambrian water and to a lesser degree with paleometeoric water. The third end member is highly radiogenic, shale-derived water which has migrated eastward from the Awati Depression to the west. Enrichment of Ca and Sr and depletion of K, Mg, and SO₄ relative to the seawater evaporation trajectory suggest waters were affected by albitization of feldspars, dolomitization, illitization of smectite, and SO₄ reduction. The mixing of meteoric water occurred subsequently to seawater evaporation, main water-rock interactions, and brine migration. The direction of brine migration is consistent with that of petroleum migration, suggesting water and petroleum have followed the same migration pathways.     

Major-ion chemistry, ��13C and 87Sr/86Sr as indicators of hydrochemical evolution and sources of salinity in groundwater in the Yuncheng Basin, China

Processes controlling hydrogeochemistry in the Yuncheng Basin, China, were characterised using major-ion chemistry, ⁸⁷Sr/⁸⁶Sr ratios and ??¹³C values. Evapotranspiration during recharge increased solute concentrations by factors of ??5?C50 in deep palaeowaters, while higher degrees of evapotranspiration have occurred in shallow, modern groundwater. Aquifer sediments (loess) contain approximately 15 weight% calcite; trends in groundwater HCO₃ concentrations and ??¹³C values (ranging from ?16.4 to ?8.2??) indicate that carbonate weathering is a significant source of DIC. Groundwater ⁸⁷Sr/⁸⁶Sr ratios (0.7110?C0.7162, median of 0.7116) are similar to those in both loess carbonate (0.7109?C0.7116) and local rainfall (0.7112), and are significantly lower than Sr in aquifer silicates (0.7184?C0.7251). Despite evidence for substantial carbonate dissolution, groundwater is generally Ca-poor (<?10% of total cations) and Na-rich, due to cation exchange. Saturation with respect to carbonate minerals occurs during or soon after recharge (all calcite and dolomite saturation indices are positive). Subsequent carbonate dissolution in the deep aquifer must occur as a second-stage process, in response to Ca loss (by ion exchange) and/or via incongruent dissolution of dolomite and impure calcite. The latter is consistent with positive correlations between ??¹³C values and Mg/Ca and Sr/Ca ratios (r ²?=?0.32 and 0.34).     

桂林地区不同类型岩溶地下水中δ13CDIC、δ18O的特征及意义

对桂林地区地下河水、岩溶大泉中的δ13CDIC、δ18O及Ca2+、Sr2+含量进行了测试分析。结果表明,地下河水的δ13CDIC值范围为–15.99‰～–12.29‰,平均值为(–14.03±1.15)‰;δ18O值范围为–6.63‰～–5.78‰,平均值为(–6.24±0.24)‰。岩溶大泉的δ13CDIC值范围为–15.26‰～–9.22‰,平均值为(–12.05±1.57)‰;δ18O值范围为–6.97‰～–3.19‰,平均值为(–5.68±0.97)‰。岩溶大泉的δ13CDIC值、δ18O值比地下河水的分别偏重1.98‰和0.56‰。通过分析发现,水的循环方式引起了不同类型地下水的同位素差异,地下河以管道流的形式进行循环,循环速度快,水岩作用时间短,碳酸盐岩碳的贡献相对较少;同时,出口处水所经历的蒸发作用时间也短,水的δ18O值偏轻。岩溶大泉以裂隙流的形式进行循环,循环速度慢,水岩作用时间长,碳酸盐岩碳的贡献相对较多;泉口处水所经历的蒸发作用时间也长,水的δ18O值偏重。Sr/Ca值与δ13CDIC值具有正相关关系,而与δ18O值的相关性差。这意味着δ13CDIC值与Sr/Ca值一样,可以在一定程度上反映出地下水的径流条件。     

Stable isotope records (δO and δC) of Lower-Middle Jurassic belemnites from the Western Balkan mountains (Bulgaria): Palaeoenvironmental application

Stable O and C isotope data of 110 Upper Pliensbachian-Lower Bajocian belemnites have been obtained and used to attempt a reconstruction of palaeotemperature and its variation in two epicontinental depositional environments from the Western Balkan mountains (Bulgaria). The samples were collected from 3 sections with high-resolution ammonite subdivision. Initially taphonomic, cathodoluminescence and geochemical analyses were used for evidence of diagenetic alteration. Non-luminescent parts of the belemnite rostra have been sampled for isotope analyses and 76 samples, having δ¹⁸O < −4‰ (PDB), δ¹³C > −0.5‰ (PDB), Fe < 250 ppm, Mn < 50 ppm, Sr > 950 ppm and Sr/Mn ratio > 80 were used for palaeotemperature interpretations. The O and C isotope data generally exhibit little stratigraphical variability with minor fluctuations, however, there are prominent positive C isotope excursions and coeval negative O isotope shifts detected in the Lower Toarcian Tenuicostatum, Falciferum and Bifrons Zones. The O isotope data, interpreted in terms of palaeotemperature, revealed relatively high seawater temperatures during the Toarcian, Aalenian and Early Bajocian, with detectable temperature rises during the Early Toarcian (maximum value of 29.6 °C). Both C isotope maxima and O isotope minima are used as evidence of the Early Toarcian anoxic event reported from many localities of the same age and in similar facies in Western Europe. In the study the latter is recognized as 3 episodes, which are closely related with the seawater temperature maxima. This isotope record pattern is considered as a consequence of a global Tethyan transgression during the Early Toarcian.     

H2O2在α-Fe2O3表面非均相氧化SO2机理的模拟研究

通过密度泛函理论模拟了H_2O_2和SO_2气体在矿物氧化物(α-Fe_2O_3)表面上的非均相反应,研究了H_2O_2和SO_2在α-Fe_2O_3(001)表面的吸附机制和氧化机制。研究结果表明,SO_2、H_2O_2均在α-Fe_2O_3(001)表面通过Fe原子进行吸附,H_2O_2相比于SO_2优先吸附在α-Fe_2O_3(001)表面,且H_2O_2在表面的赋存形式趋向于两个·OH形式吸附。通过二者共吸附的局域态密度、差分电荷密度、Mulliken电荷布局分析结果发现,SO_2和H_2O_2的共吸附形式是通过H_2O_2产生的·OH吸附在α-Fe_2O_3(001)表面,同时SO_2被H_2O_2产生的·OH氧化[S(SO_2)-电荷布局:0. 79 e→1. 32 e; O(H_2O_2)-电荷布局:-0. 77 e→-1. 11 e]形成·OH+SO_2团簇。模拟结果表明大气微量气体H_2O_2能够在矿物氧化物表面介导SO_2吸附并促进SO_2的转化,为理解H_2O_2在大气中非均相氧化SO_2的反应过程提供了理论依据。     

Sr/Ca,Mg/Ca:珊瑚岛鸟粪沉积的物源指示计*

文章尝试用Sr/Ca,Mg/Ca比值作物源指示计,区分了珊瑚岛屿受到海鸟粪影响的湖泊沉积物中鸟粪、珊瑚砂、植物这几种主要的环境介质对沉积物的相对贡献,据此恢复1800年来西沙群岛东岛海鸟数量变化和植被演化的历史。结果表明,东岛海鸟数量的变化历史可划分为潜伏期、增长期、稳定期和衰退期4个阶段,历史时期东岛海鸟生态系统的建立和发展与岛屿植被的演变有着密切的联系。研究获得的方法和初步结论为进一步开展西沙岛屿海鸟数量变化、植被演化的广泛对比并探讨与气候变化、人类活动的相互联系提供了基础。     

浙江省常山县上震旦统西峰寺组碳酸盐的δ13C和δ18O测定

作者对浙江省常山县三里亭北九家坞的上震旦统剖面的碳酸盐系统采集的54个样品,作了碳、氧稳定同位素的分析。其中δ¹³C除4个外几乎全为正值,平均值2.16%,这与前人提到过的文德期以δ¹³C负迁移为特征的结论不符。离散变为9.0。最大负峰值出现在剖面近中部的磷块岩层中,可能与海流状况的剧变有关。δ¹⁸O除最末两个为小的正值外,几乎全为负值。