A paleotemperature record derived from dissolved noble gases in groundwater of the Aquia Aquifer (Maryland, USA)

Low ¹⁴C activities in groundwater of the confined part of the Aquia aquifer in southeastern Maryland suggest that most of this water infiltrated at least 30,000 years ago. However, radiocarbon contents of the dissolved inorganic carbon seem to be affected by isotopic exchange, possibly with secondary calcite deposits in the formation, leading to overestimated ¹⁴C ages. Whereas the geochemistry of the Aquia aquifer complicates the application of the widely used ¹⁴C dating method, the accumulation of radiogenic He seems to provide a viable alternative for establishing a chronology. The quasi-linear increase of He concentrations with flow distance observed in the Aquia aquifer can be explained entirely by accumulation of in situ produced radiogenic He. U and Th concentrations in Aquia sand were measured in order to determine the accumulation rate of ⁴He with sufficient confidence to establish a He time scale.Concentrations of dissolved atmospheric noble gases were used to derive mean annual ground temperatures at the time of infiltration. These noble gas temperatures (NGTs) clearly show the presence of water that infiltrated under much cooler conditions than at present. NGTs are correlated with chloride concentrations, corroborating the hypothesis that chloride variations in this aquifer constitute a climate signal. In contrast, the stable isotope ratios δ¹⁸0 and δD do not provide a clear record of past climatic changes in the Aquia aquifer and the correlation between NGTs and stable isotope ratios is weak. The NGT record suggests that mean annual temperatures in this midlatitude coastal site during the last glacial maximum (LGM) were (9.0 ± 0.6) °C colder than during the Holocene. This difference is slightly lower than estimates derived from pollen data for this region, but considerably larger than the rather uniform cooling of about 5°C indicated by noble gas studies in more southern locations of North America. The larger cooling is ascribed to the influence of the Laurentide ice sheet, which at its maximum extension came as close as 250 km to our study site.     

Noble gases reveal the complex groundwater mixing pattern and origin of salinization in the Azraq Oasis,Jordan

Azraq Oasis in the eastern Jordanian desert is an important freshwater resource of the country. Shallow groundwater reserves are heavily exploited since the 1980s and in consequence the groundwater table dropped significantly. Furthermore, some wells of the major well field drilled into the shallow aquifer show an increasing mineralization over the past 20 years. A previous study using conventional tracers did not result in a satisfactory explanation, from where the salt originates and why only a few wells are affected. In this study, the application of dissolved noble gases in combination with other tracer methods reveals a complex mixing pattern leading to the very localized salinization within the well field. It is found that primarily the wells affected by salinization 1) contain distinctly more radiogenic ⁴He than the other wells, indicating higher groundwater age, and 2) exhibit ³He/⁴He ratios that argue for an imprint of deep fluids from the Earth's mantle.However, the saline middle aquifer below is virtually free of mantle helium, which infers an upstream from an even deeper source through a nearby conductive fault. The local restriction of the salinization process is explained by the wide range of permeabilities of the involved geologic units. As the wells abstract water from the whole depth profile, they initially pump water mainly from the well conductive top rock layer. As the groundwater table dropped, this layer fell progressively dry and, depending on the local conductivity profile, some wells began to incorporate more water from the deeper part of the shallow aquifer into the discharge. These are the wells affected by salinization, because according to the presented scheme the deep part of the shallow aquifer is enriched in both salt and mantle fluids.     

河北平原第四系地下水氦同位素特征

通过对河北平原第四系地下水He同位素进行比较分析,根据过剩He(4Heexc)、3He/4He比值、δ3He值分析认为,河北平原第四系地下水He同位素有5个特征:(1)地下水中过剩He浓度沿着地下水的流向而增高;(2)地下水中的过剩He浓度随着地下水埋深加大而增高;(3)满城—沧州剖面上过剩He浓度大于石家庄—衡水剖面上的过剩He浓度;(4)河北平原第四系地下水主要是由大气降水补给的;(5)衡水热水过剩He浓度很高(>674 83×10-8cm3STPg-1),这表明以放射成因He为主,地幔成因的He极少。另外地下水的3He/4He比值、R/Ra、δ3He值是判断氦源的一个灵敏的指示剂。     

Identification of He sources and estimation of He ages in groundwater of the North China Plain

Dissolved helium concentrations and ³He/⁴He ratios were measured for 18 groundwater samples collected from the Quaternary confined aquifers in the North China Plain (NCP). The dissolved helium concentrations ranged from 1 × 10⁻⁷ to 1 × 10⁻⁶ cm³STP·g⁻¹ in the 14 samples from the central plain, but was approximately two orders of magnitude higher, between 6 × 10⁻⁶ and 9 × 10⁻⁵ cm³STP·g⁻¹, in 4 samples from the coastal plain. Based on these concentrations and the corresponding ³He/⁴He ratios varying from 0.09 to 0.55 R_a (where R_a is the ³He/⁴He ratio of air), the dissolved helium in groundwater in the central plain was identified to be primarily a mixture of atmospheric helium with radiogenic helium and a representative radiogenic helium ratio was estimated to be 0.035 R_a. Despite the high fraction of terrigenic ⁴He in the samples from the coastal plain, their ³He/⁴He ratios were found to be significantly above this radiogenic value, ranging between 0.20 and 0.37 R_a, indicating the presence of a mantle-derived He component in this area. About 2–4% mantle helium was estimated to be present in the groundwater of the coastal plain, which probably is associated with the regional Cangdong fault and tectonic activities. Based on the radiogenic He component, ⁴He ages of the groundwater in the central plain were calculated by assuming either pure in situ production or an external helium flux J₀ of 4.7 × 10⁻⁸ cm³STPcm⁻²a⁻¹. The estimated ⁴He ages fall between 9.5 and 51.4 ka and are comparable to the ¹⁴C ages, suggesting that the results of ⁴He dating are reasonable and can be an effective tool to estimate groundwater residence times under suitable conditions.     

Experimental investigations on the formation of excess air in quasi-saturated porous media

The formation of an excess of dissolved gas (“excess air”) in quasi-saturated media was studied by analyzing and interpreting dissolved noble gas concentrations in laboratory column experiments. Using quartz sand filled columns of 1 m length, two different experimental designs were realized. In the first, groundwater recharge was simulated by a unidirectional vertical water flow through the columns. In the second, groundwater level fluctuations in an aquifer zone without active infiltration were reproduced by cyclic water level fluctuations in the columns. The reproducible generation of excess air under these defined, near natural conditions was successful. Partial or complete dissolution of air bubbles entrapped in the quartz sand could be identified as the mechanism responsible for the generation of excess air. Depending on the experimental design, supersaturation of the dissolved atmospheric noble gases ranging between 1.4% ΔNe and 16.2% ΔNe was found. The measured noble gas patterns were interpreted using inverse modeling and conceptual gas exchange models and were compared to results of numerical simulations of gas bubble dissolution in water filled soil columns. The gas composition in most of the samples resembles either unfractionated pure atmospheric excess air or is fractionated in accordance with closed-system equilibration between entrapped air and surrounding water. In addition to the amount of entrapped air, the hydrostatic pressure exerted on the entrapped air bubbles is the dominating parameter responsible for the total amount of dissolved air. The composition of the excess air component is controlled by the water flow regime, the bubble size distribution, the initially dissolved gas concentrations and the initially entrapped gas composition.     

Tritium�Chelium groundwater age used to constrain a groundwater flow model of a valley-fill aquifer contaminated with trichloroethylene (Quebec, Canada)

Tritium?Chelium groundwater dating was carried out in a trichloroethylene (TCE)-contaminated valley-fill aquifer system in Quebec, Canada, where a numerical groundwater flow model was developed. Forty seven discrete groundwater and dissolved gas samples were obtained along two flow paths originating from known TCE source zones whose related plumes converge down gradient to form a single plume. Sampling points in monitoring wells were projected onto vertical sections showing particle tracks along the two flow paths. At these points, simulated advective ages obtained from particle tracking were matched to tritium?Chelium ages using different porosity values; the best match was 0.35. Ages were also obtained above and below a prodeltaic silty aquitard in a portion of the aquifer where some source zones are located, which provide groundwater and TCE transit times through the aquitard as well as a mean vertical hydraulic conductivity that agrees with previous estimates used in the model. In certain locations, anomalously old ages associated with high terrigenic ⁴He indicate areas where groundwater from the underlying proglacial unit flows upward into the deltaic sand aquifer through aquitard windows. Upflow locations correspond with increased TCE concentrations, suggesting significant TCE provenance through the proglacial unit originating from a previously unrecognized TCE source zone.     

Source identification of methane in groundwater in shale gas development areas: A critical review of the state of the art,prospects, and future challenges

Shale gas exploration and development carry the risk of causing groundwater contamination and enhancing the greenhouse effect through methane leakage. Identifying the source of abnormal methane in groundwater of shale gas development areas is becoming a research hotspot in the fields of groundwater and climate change. This paper reviews the traditional methodology in identifying sources of methane and its deficiency in groundwater application. Then potential and advantages of using noble gases were discussed on how to overcome these limitations of the traditional method. Finally, based on noble gas, the current application status and future challenges of methane source identification in groundwater were analyzed. It can be summarized as:(1) due to chemical and/or microbial processes in the aquifer system, the traditional methodology for methane source identification, which utilizes molecular and isotopic compositions of hydrocarbon gas, has multiple interpretationsand large uncertainties;(2) the non-reactive nature and well-characterized isotopic compositions of noble gases in the atmosphere, hydrosphere, and crust, make noble gases ideal indicators of the sources of methane in groundwater. Moreover, the mechanism of formation and release of crustal noble gas prevent shale gas signatures from being interfered with by natural gas;(3) the key scientific tasks surrounding the use of noble gases for methane source identification include quantitatively separating the components of atmosphere-derived, mantle-derived, and crust-derived noble gases from the bulk noble gases in groundwater. It quantifies the solubility fractionation of noble gases induced by water-gas interaction during methane migration to the aquifer. The application of noble gases can bring a new perspective to tracing the source of methane in groundwater and is of great significance to the protection of groundwater quality in shale gas development areas and mitigation of climate change.     

Application of the chlorine-36 method for the delineation of groundwater infiltration of large river systems: example of the Danube River in western Hungary (Szigetköz area)

The gravel aquifer within the Szigetköz Plain in northern Hungary is mainly fed by the infiltration of the Danube River. This infiltration process can be identified using the tritium/helium method to a distance of about 30 km away from the infiltration area of the Danube. In this study, chlorine-36 analyses are used as additional method. This natural radioisotope was also produced by nuclear bomb tests in the atmosphere. It is an ideal, stable constituent for this particular study due to its very long half-life (300,000 years), and consequently acts as an independent check of the established model of aquifer recharge. The chlorine-36 data of the analysed selected groundwater samples of this area clearly show the effect of the atmospheric nuclear bomb tests, with enhanced ³⁶Cl/Cl ratios of up to a factor 10 higher than the unaffected groundwater of the pre-bomb period within the study area. Finally, the observed ³⁶Cl values were introduced into a transport model with dispersion/advection-type flow of groundwater to deduce the transport parameters.     

Dynamic changes in hydrogeochemical conditions caused by tunnel excavation at the Aspo Hard Rock Laboratory (HRL), Sweden

Hydraulic changes caused by tunneling at the Aspo Hard Rock Laboratory (HRL) in Sweden have been investigated over a period of 2a using different hydrochemical approaches, i.e. noble gas content, isotopic measurements and major ion concentrations. The dissolved noble gases (⁴He and Ne contents, and the ratio of ³He/⁴He, ⁴⁰Ar/³⁶Ar), stable isotopes, chemical concentrations of major ions, and ³⁶Cl/Cl ratios, were determined in groundwater samples collected in the tunnel from borehole sections isolated by inflated packers. Groundwater was categorized into 3 groups based on ⁴He and Cl⁻ contents: undisturbed groundwater (i.e. prior to tunnel construction) with high ⁴He and Cl⁻ contents, groundwater that has been gradually changed by mixing with Baltic seawater and whose ⁴He and Cl⁻ contents have gradually increased with increasing depth, and groundwater that has been totally changed due to a rapid mixing of Baltic seawater and/or shallow groundwater and whose ⁴He and Cl⁻ contents are extremely low compared with other samples collected at the same surrounding depth. The oldest groundwater with a high salinity of more than 14,000 mg l⁻¹ of Cl⁻ is estimated to be more than 1.8 Ma old. The groundwater residence time ranges from 0.9 to 900 Ka in the mixing-zone. Groundwater in the disturbed zone where rapid mixing has occurred is hard to date reliably and its primary hydrochemical character has already been lost.     

Noble gas tracing of groundwater/coalbed methane interaction in the San Juan Basin, USA

The San Juan Basin natural gas field, located in northwestern New Mexico and southwestern Colorado in the USA, is a case-type coalbed methane system. Groundwater is thought to play a key role in both biogenic methane generation and the CO₂ sequestration potential of coalbed systems. We show here how noble gases can be used to construct a physical model that describes the interaction between the groundwater system and the produced gas. We collected 28 gas samples from producing wells in the artesian overpressured high production region of the basin together with 8 gas samples from the underpressured low production zone as a control. Stable isotope and major species determination clearly characterize the gas in the high production region as dominantly biogenic in origin, and the underpressured low producing region as having a significant admix of thermogenic coal gas. ³He/⁴He ratios increase from 0.0836R_a at the basin margin to 0.318R_a towards the center, indicating a clear but small mantle He signature in all gases. Coherent fractionation of water-derived ²⁰Ne/³⁶Ar and crustal ⁴He/⁴⁰Ar* are explained by a simple Rayleigh fractionation model of open system groundwater degassing. Low ²⁰Ne concentrations compared to the model predicted values are accounted for by dilution of the groundwater-associated gas by desorbed coalbed methane. This Rayleigh fractionation and dilution model together with the gas production history allows us to quantify the amount of water involved in gas production at each well. The quantified water volumes in both underpressured and overpressured zones range from 1.7 × 10³ m³ to 4.2 × 10⁵ m³, with no clear distinction between over- and underpressured production zones. These results conclusively show that the volume of groundwater seen by coal does not play a role in determining the volume of methane produced by secondary biodegradation of these coalbeds. There is no requirement of continuous groundwater flow for renewing the microbes or nutrient components. We furthermore observe strong mass related isotopic fractionation of ²⁰Ne/²²Ne and ³⁸Ar/³⁶Ar isotopic ratios. This can be explained by a noble gas concentration gradient in the groundwater during gas production, which causes diffusive partial re-equilibration of the noble gas isotopes. It is important for the study of other systems in which extensive groundwater degassing may have occurred to recognize that severe isotopic fractionation of air-derived noble gases can occur when such concentration gradients are established during gas production. Excess air-derived Xe and Kr in our samples are shown to be related to the diluting coalbed methane and can only be accounted for if Xe and Kr are preferentially and volumetrically trapped within the coal matrix and released during biodegradation to form CH₄.     

穆兴平原北部地下水年龄及更新性

地下水年龄结构是了解一个地区地下水资源开采可持续性的重要基础。穆兴平原地下水开采量增加以及地下水环境恶化,对该地区可持续发展有一定制约,为此在2016年采集CFCs样品31组和3H样品60组,估算了研究区地下水年龄。结果表明,穆兴平原北部地下水年龄为21年到大于65年,由西北部和穆棱河向平原中部及乌苏里江逐渐变老,更新性变差,主要受到大气降水和地表河水补给,但是由于地表覆盖一层黏性土,地下水中缺失小于10年的水;不同井深样品中二者及NO_3~-浓度的变化,表明在60 m以上地下水的防污性能较差,而在100 m以下则较好,饮用水源井深需超过100 m。     

The behaviour of boron isotopes in natural waters and in water–rock interactions

The wide boron isotopic variations occurring in natural waters mainly are derived from the 20‰ fractionation between dissolved boric acid and borate anions, associated with the preferential removal from the system of ¹¹B depleted borate ions by adsorption and/or minerals formation. Typical adsorbants of boron dissolved in groundwater are clay minerals of the aquifer matrix. Boron (and strontium) isotopes were used in investigating two alluvial aquifers in Tuscany, where boron concentration is often above 1 mg L^− 1 and may attain 8 mg L^− 1. The isotopic results indicate that, in the first case (Cecina River basin), the boron contamination is anthropogenic and derives from past discharge into streams of boron-rich industrial wastes. In the second case (Cornia Plain), the dissolved boron is released by boron-rich clayey sediments of the aquifer matrix and has, therefore, a natural origin.     

Dissolved noble gases in the porewater of lacustrine sediments as palaeolimnological proxies

This paper presents results from the numerical modelling of the transport of atmospheric noble gases (He, Ne, Ar, Kr, Xe), tritiated water and ³He produced by radioactive decay of ³H, in unconsolidated lacustrine sediment. Two case studies are discussed: (1) the evolution of ³H and ³He concentrations in the sediment porewater of Lake Zug (Switzerland) from 1953 up to the present; and (2) the response of dissolved atmospheric noble gas concentrations in the sediment porewater of a subtropical lake to an abrupt climatic change that occurred some 10 kyr before the present. (1) Modelled ³H and ³He porewater concentrations are compared with recent data from Lake Zug. An estimate of the effective diffusion coefficients in the sediment porewater is derived using an original approach which is also applicable also to lakes for which the historical ³H and ³He concentrations in the water column are unknown. (2) The air/water partitioning of atmospheric noble gases is sensitive to water temperature and salinity, and thus provides a mechanism by which these environmental variables are recorded in the concentrations of atmospheric noble gases in lakes. We investigate the feasibility of using noble gas concentrations in the porewater of lacustrine sediments as a proxy for palaeoenvironmental conditions in lakes. Numerical modelling shows that heavy noble gases in sediment porewater, because of their comparatively small diffusion coefficients and the strong temperature sensitivity of their equilibrium concentrations, can preserve concentrations corresponding to past lake temperatures over times on the order of 10 kyr. Noble gas analysis of sediment porewaters therefore promises to yield valuable quantitative information on the past environmental states of lakes.     

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius.Vesuvius groundwaters are dilute (mean TDS ∼ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. δD and δ¹⁸O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or ¹⁸O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO₂-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions.The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both ¹³C/¹²C and ³He/⁴He measurements indicate the contribution of a magmatic component with a δ¹³C ∼ 0‰ and R/R_a of ∼2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts.A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO₂ release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata-Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO₂ depleted, despite in some cases containing significant concentrations of magma-derived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.     

确定平原地下水4He年龄方法的尝试

放射性衰变产生的氦组分（3H衰变质产生3He，U/Th衰变产生4He）广泛地用水地下水测年。本文分析了地下水中惰性气体的组成，采用过剩空气非分馏（UA）模型进行了单独氦组分的分离。结果表明，河北平原第三含水组（Q2）中的过剩4He是含水组内原地内原地产量和深部地壳通量的共同作用的结果。由于缺乏确定氦平衡参数的约束很好的客观分析，选择应用地下水流模型主观调节来估算迭代过程中的外部通量和流速场，然后根据这个模型所取得的4He年龄与应用其他方法包括14C测年和水文模型取得的年龄进行了对比。     

Dating groundwater in the Bohemian Cretaceous Basin: Understanding tracer variations in the subsurface

The northern section of the Bohemian Cretaceous Basin has been the site of intensive U exploitation with harmful impacts on groundwater quality. The understanding of groundwater flow and age distribution is crucial for the prediction of the future dispersion and impact of the contamination. State of the art tracer methods (³H, ³He, ⁴He, ⁸⁵Kr, ³⁹Ar and ¹⁴C) were, therefore, used to obtain insights to ageing and mixing processes of groundwater along a north–south flow line in the centre of the two most important aquifers of Cenomanian and middle Turonian age. Dating of groundwater is particularly complex in this area as: (i) groundwater in the Cenomanian aquifer is locally affected by fluxes of geogenic and biogenic gases (e.g. CO₂, CH₄, He) and by fossil brines in basement rocks rich in Cl and SO₄; (ii) a thick unsaturated zone overlays the Turonian aquifer; (iii) a periglacial climate and permafrost conditions prevailed during the Last Glacial Maximum (LGM), and iv) the wells are mostly screened over large depth intervals.Large disagreements in ⁸⁵Kr and ³H/³He ages indicate that processes other than ageing have affected the tracer data in the Turonian aquifer. Mixing with older waters (>50 a) was confirmed by ³⁹Ar activities. An inverse modelling approach, which included time lags for tracer transport throughout the unsaturated zone and degassing of ³He, was used to estimate the age of groundwater. Best fits between model and field results were obtained for mean residence times varying from modern up to a few hundred years. The presence of modern water in this aquifer is correlated with the occurrence of elevated pollution (e.g. nitrates).An increase of reactive geochemical indicators (e.g. Na) and radiogenic ⁴He, and a decrease in ¹⁴C along the flow direction confirmed groundwater ageing in the deeper confined Cenomanian aquifer. Radiocarbon ages varied from a few hundred years to more than 20 ka. Initial ¹⁴C activity for radiocarbon dating was calibrated by means of ³⁹Ar measurements. The ¹⁴C age of a sample recharged during the LGM was further confirmed by depleted stable isotope signatures and near freezing point noble gas temperature. Radiogenic ⁴He accumulated in groundwater with concentrations increasing linearly with ¹⁴C ages. This enabled the use of ⁴He to validate the dating range of ¹⁴C and extend it to other parts of this aquifer. In the proximity of faults, ³⁹Ar in excess of modern concentrations and ¹⁴C dead CO₂ sources, elevated ³He/⁴He ratios and volcanic activity in Oligocene to Quaternary demonstrate the influence of gas of deeper origin and impeded the application of ⁴He, ³⁹Ar and ¹⁴C for groundwater dating.     

Intercomparison of tritium and noble gases analyses, 3H/3He ages and derived parameters excess air and recharge temperature

Groundwater age dating with the tritium–helium (³H/³He) method has become a powerful tool for hydrogeologists. The uncertainty of the apparent ³H/³He age depends on the analytical precision of the ³H measurement and the uncertainty of the tritiogenic ³He component. The goal of this study, as part of the groundwater age-dating interlaboratory comparison exercise, was to quantify the analytical uncertainty of the ³H and noble gas measurements and to assess whether they meet the requirements for ³H/³He dating and noble gas paleotemperature reconstruction.Samples for the groundwater dating intercomparison exercise were collected on 1 February, 2012, from three previously studied wells in the Paris Basin (France). Fourteen laboratories participated in the intercomparison for tritium analyses and ten laboratories participated in the noble gas intercomparison. Not all laboratories analyzed samples from every borehole.The reproducibility of the tritium measurements was 13.5%. The reproducibility of the ³He/⁴He ratio and ⁴He, Ne, Ar, Kr and Xe concentrations was 1.4%, 1.8%, 1.5%, 2.2%, 2.9%, and 2.4% respectively.The uncertainty of the tritium and noble gas measurements results in a typical ³H/³He age precision of better than 2.5 years in this case. However, the measurement uncertainties for the noble gas concentrations are insufficient to distinguish the appropriate excess air model if the measured helium concentration is not included. While the analytical uncertainty introduces an unavoidable source of uncertainty in the ³H/³He apparent age estimate, other sources of uncertainty are often much greater and less well defined than the analytical uncertainty.     

Upwelling of Mantle-derived Material in Southeast China: Evidence from Noble Gas Isotopes

Shallow groundwater collected in Chaozhou,Huizhou,and Guangzhou allowed testing of concentrations and the isotope ratios of noble gases.Based on the calculated noble gas temperature(NGT)and the ratio of noble gas isotopes,the recharge temperature,recharge source,and residence time of groundwater can be calculated.In addition,the contribution of noble gas components from different sources to the sample components can be assessed.In the Huizhou area,according to the 1/Xe vs.Ne/Xe and NGT data,the shallow sandstone-confined water samples in the Shiba area and the unconfined water samples of the Huangshadong are in different temperature ranges,indicating that they have different recharge sources,both in time or space.The He components in the samples are calculated to obtain the content of radiogenic ⁴He in the crust and to simulate the groundwater ages.The noble gas isotope ratios show the addition of mantle components into the basalt aquifers and sandstone aquifers in Chaozhou and Huizhou.Except for atmospheric and crustal sources,there is a certain proportion of mantle-derived components in the shallow underground cold water in Huizhou and Chaozhou.The noble gases in the Chaozhou groundwater have an obvious mantle signature,allowing speculation that there is a deep fluid carrying mantle characteristics.This upwelling of mantle-derived material might be caused by the India-Eurasia collision or that between the Philippine Sea Plate and the Eurasian Plate.     

涞源北盆地地下水氢氧同位素特征及北海泉形成模式

拒马源泉群作为拒马河的源头,受到了较多专家和学者的关注。但这些研究多集中在地下水的水化学、水位动态、泉流量等特征上,对地下水氢氧同位素特征的分析几乎没有,且对北海泉的成因解释多为粗略的定性概述。为了说明涞源北盆地地下水的氢氧同位素特征,详细揭示北海泉的形成模式,首次系统地采集了不同含水岩组的地下水样品,测定了水样的氢氧同位素组分。结果表明:样品点δD和δ18O值均落在区域大气降水线上或附近,大气降水是研究区地下水的主要补给来源;白云岩、灰岩含水岩组高程效应较明显,径流途径长,松散含水层径流途径短,受蒸发作用较强;白云岩、灰岩含水岩组和松散含水层氘盈余d值分别为6.0‰～11.6‰、4.2‰～11.2‰、3.8‰～8.0‰,较大气降水大部分偏小,表明岩溶水和松散孔隙水经历了不同的流动过程;白云岩、灰岩含水岩组从补给区向排泄区各自流动过程中,在小西庄、香炉屯村附近断裂带发生沟通混合,然后在向盆地中心径流过程中受断层阻水上升,上升过程中又接受了松散孔隙水的补给,最后在松散岩层中出露成泉,形成北海泉。在孔隙水混入前,两者的平均补给比例大约为48.4%～57.6%和42.4%～51.6%。     

Flow of river water into a Karstic limestone aquifer. 1. Tracing the young fraction in groundwater mixtures in the Upper Floridan Aquifer near Valdosta, Georgia

The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl⁻, ³H, tritiogenic helium-3 (³He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O₂ (DO), H₂S, CH₄, δ¹⁸O, δD, and ¹⁴C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl⁻, δ¹⁸O, δD, CFC-12, and the quantity (³H+³He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H₂S, CH₄, ¹⁴C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl⁻ and δ¹⁸O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ¹⁸O=−2.5±0.3‰, Cl⁻=12.2±2 mg/l), (2) regional infiltration water (δ¹⁸O=−4.2±0.1‰, Cl⁻=2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ¹⁸O=−3.4±0.1‰, Cl⁻=2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.