The geochemistry and mixing of leakage in a semi-confined aquifer at a municipal well field,Memphis, Tennessee,USA

The Memphis aquifer in southwestern Tennessee is confined to a semi-confined unconsolidated sand aquifer and is the primary municipal water source in the Memphis metropolitan area. Past studies have identified regions in the metropolitan area in which the overlying upper Claiborne confining unit lacks significant clay and provides a hydraulic connection between the shallow aquifer and the Memphis aquifer. In this study, major solute chemistry, ³H, and ³H/³He groundwater dating are used to investigate the extent and chemical effects of leakage through the confining unit to the Memphis aquifer in the vicinity of a municipal well field. The ³H/³He dates and geochemical modeling of the chemical data are used to constrain mixing fractions and the timing of modern recharge. Tritium activities of as much as 2.8 TU are observed in shallow production wells, but deeper production wells have ³H activities that approach the detection limit. Trends in water chemistry indicate vertical mixing in the aquifer of shallow Na–SO₄–Cl-rich water and deeper Ca–Mg–HCO₃-rich water. Water chemistry does not vary consistently with seasonal pumping, but ³H activity generally decreases during low use periods. Stable O and H isotopes show little variation and are not useful groundwater tracers for this study. The ³H-bearing, Na–SO₄–Cl-rich water is interpreted to reflect recharge of modern water through the upper Claiborne confining unit. The ³H/³He dates from 5 production wells indicate modern recharge, that infiltrated 15–20 a ago, is present in the shallow production wells. Geologic data and hydrologic boundary conditions suggest that the most likely source for continued leakage is a nearby stream, Nonconnah Creek. Geochemical reaction modeling using the NETPATH computer code suggests that proportions of shallow aquifer water leaking into the Memphis aquifer range from 6 to 32%. The ³H/³He dating and NETPATH modeling results correlate well, suggesting that these complementary analytical tools provide an effective means to evaluate proportions of modern water leaking into semi-confined aquifers. These results also indicate a need to carefully consider connections between surface water and semi-confined groundwater resources in wellhead protection programs.     

Spallation production of 3He, 21Ne,and 38Ar from target elements in the Bruderheim chondrite

The concentrations of noble gas isotopes of He, Ne and Ar have been measured in eight mineral separates of the Bruderheim chondrite. The cosmic-ray-produced nuclides ²¹Ne and ³⁸Ar were correlated by a computer least-squares fitting program with the elemental composition in each separate of potential targets for nuclear production yielding the following production equations: $\text{[}{}^{21}\text{Ne, 10}{}^{\mathrm{?8}}\text{cm}{}^3\text{/g] = k(0.45[Mg] + 0.085[Si] + 0.060[S] + 0.017[Ca] + 0.0044[Fe + Ni])}$; $\text{[}{}^{38}\text{Ar, 10}{}^{\mathrm{?8}}\text{cm}{}^3\text{/g] = k(2.6[K] + 0.37[Ca] + 0.08[Ti + Cr + Mn] + 0.021[Fe + Ni])}$ with elemental concentrations in weight per cent and k equal to the reciprocal of the cosmic-ray exposure age of Bruderheim. The P(S)/P(Cr + Mn + Fe + Ni) weight production ratio for ³He was determined to be 1.53; relative productions of ³He from O, Mg and Si and ²¹Ne from Al proved to be incalculable.     

Particle mixing rates in sediments of the eastern equatorial Pacific: Evidence from 210Pb, 239,240Pu and 137Cs distributions at MANOP sites

Particle mixing rates (D_B) calculated from excess ²¹⁰Pb gradients in sediments of the east equatorial Pacific range from 0.04 to 0.5 cm²/y, with variation of a factor of 3–4 at a single site. Diffusion of the ²³⁶Ra daughter ²²²Rn may affect ²¹⁰Pb distributions under conditions of slow mixing and low ²¹⁰Pb flux to the seafloor, as shown by a siliceous ooze-clay core which contained the fallout radionuclides ^239,240Pu and ¹³⁷Cs but no excess ²¹⁰Pb (relative to ²²⁶Ra). There is no clear relationship between ²¹⁰Pbderived mixing rates and sediment type, accumulation rate or organic carbon flux to the sediments. Comparison of ²¹⁰Pb mixing rates with those calculated from ^239,240Pu and ¹³⁷Cs distributions reveals better agreement for a pulse input of the fallout radionuclides (D_B = 0.03?0.4 cm²/y) than for continuous input at a constant rate (D_B = 0.1?1.6 cm²/y), although the Pu and ¹³⁷Cs data are better fit by the latter model. The agreement may be fortuitous because ^239,240Pu and ¹³⁷Cs appear significantly deeper than ²¹⁰Pb in at least one core. Tracer separation could be caused by particle size-selective mixing by the benthic fauna or by chemical mobilization. If the fallout radionuclides are scavenged from surface waters by large, organic-rich particles such as fecal pellets, their release and migration may result from decomposition of the carrier in surface sediments. Either a relatively unreactive form of Pu (e.g. oxidized Pu) has been released by this process or a one-dimensional model is inadequate to explain its observed penetration into the sediments. Activity ratios of ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ in the sediments decrease with increasing north latitude, and the trend reflects higher fluxes of ^239,240Pu near the weapons test site at Christmas Island (2°N). The ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ ratios and fluxes to the sediment (assuming constant input) at the siliceous ooze-red clay site are consistent with published sediment trap data from a nearby site. Thus if fallout radionuclide fluxes to the sea floor were higher in the past, both ^239,240Pu and ¹³⁷Cs have been released from sinking particles.     

松辽盆地青山口组橄榄粗安岩：40Ar/39Ar年龄、地球化学及其成盆、成烃和成藏意义

在松辽盆地上白垩统青山口组二段湖相泥岩中识别出橄榄粗安岩夹层,高精度⁴⁰Ar/³⁹Ar坪年龄t_p=88.0±0.3Ma,属晚白垩世Coniacian阶。岩石具玻基少斑斑状结构,斑晶为橄榄石、辉石和斜长石。岩石富钠、富铝、富轻稀土（∑LREE/∑HREE=8.0~9.7）和U、Th、Pb、Rb、Sr、Ba等不相容的大离子亲石元素,Rb/Sr比高、Sm/Nd比低,δEu =0.95~1.36,高镁（Mg^#=0.61~0.64）,高氧化度（Ox^o=0.62~0.68）,低分异指数（MDI=3.4~5.3）。MgO/Al₂O₃和标准矿物压力计算得到岩浆源区深度大于60km。岩浆源于富集型地幔,属板内火山岩,是成盆过程中裂谷作用发育到最大深切割期的产物。火山活动热效应及其高区域地温场有利于成烃,造成局部类礁相环境形成的大量生物灰岩沉积是重要烃源岩,火山岩之下的牵引构造、之上的差异压实局部高部位以及其周围的浊积体是成藏有利部位。     

Helium accumulation in groundwater,I: An evaluation of sources and the continental flux of crustal 4He in the Great Artesian Basin,Australia

The rate of accumulation of ⁴He in the groundwaters of the J-aquifer of the Great Artesian Basin, Australia has been determined using ¹⁴C and hydrologic ages. For groundwaters less than 50 Kyr in age, the ⁴He accumulation rate is 4.6 × 10^?12 HeAU (where ) in close agreement with in-situ production rate of ⁴He (3.95 × 10^?12 HeAU) based on U and Th concentrations of 1.7 and 6.1, respectively, of the sandstone. For groundwaters older than 100 Kyr, the rate of ⁴He accumulation is 2.91 × 10^?10 HeAU based on hydrologic ages; or 74 × the rate of in-situ production. The rate of ⁴He “production” due to weathering of the aquifer rock is calculated to be ~10^?16 HeAU, indicating that the weathering input of ⁴He is insignificant. If the groundwater of the GAB can be considered as a trap for the total crustal production of ⁴He, the rate of ⁴He accumulation under a steady-state flux is calculated to be 3.02 × 10^?10 HeAU, in agreement with the measured accumulation rate. It is concluded that over long times the ⁴He accumulation rate in groundwater aquifers may be controlled by the whole crust flux of ⁴He.     

The mixing properties of melts and glasses in the system NaAlSi3O8-KAlSi3O8: Comparison of experimental data obtained by knudsen cell mass spectrometry and solution calorimetry

The apparent differences between heats of mixing determined by solution calorimetric measurements on quenched samples in the system NaAlSi₃O₈-KAlSi₃O₈ and heats of mixing determined at high temperatures by Knudsen cell mass spectrometry are caused by thermal effects related to the glass transition. When these effects are allowed for, the calorimetric data and Knudsen cell measurements are in good agreement.     

Storm pulse chemographs of saturation index and carbon dioxide pressure: implications for shifting recharge sources during storm events in the karst aquifer at Fort Campbell,Kentucky/Tennessee,USA

Continuous records of discharge, specific conductance, and temperature were collected through a series of storm pulses on two limestone springs at Fort Campbell, western Kentucky/Tennessee, USA. Water samples, collected at short time intervals across the same storm pulses, were analyzed for calcium, magnesium, bicarbonate, total organic carbon, and pH. Chemographs of calcium, calcite saturation index, and carbon dioxide partial pressure were superimposed on the storm hydrographs. Calcium concentration and specific conductance track together and dip to a minimum either coincident with the peak of the hydrograph or lag slightly behind it. The CO₂ pressure continues to rise on the recession limb of the hydrograph and, as a result, the saturation index decreases on the recession limb of the hydrograph. These results are interpreted as being due to dispersed infiltration through CO₂-rich soils lagging the arrival of quickflow from sinkhole recharge in the transport of storm flow to the springs. Karst spring hydrographs reflect not only the changing mix of base flow and storm flow but also a shift in source of recharge water over the course of the storm.

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Resumen Se ha registrado en continuo la descarga, conductancia específica y temperatura de una serie de episodios de tormenta en dos manantiales en calizas ubicados en Fort Campbell, en el oeste de Kentucky/Tennessee (Estados Unidos de América). Se ha analizado muestras de agua recogidas en breves intervalos de tiempo durante los episodios de tormenta, determinando el calcio, magnesio, bicarbonato, carbono orgánico total y pH. Se ha superpuesto quimiogramas de calcio, índice de saturación en calcita y presión parcial de dióxido de carbono en los hidrogramas de las tormentas. La concentración de calcio y la conductancia específica se comportan de forma similar y presentan un mínimo que coincide también con un pico del hidrograma o que se retrasa ligeramente con respecto a él. La presión de dióxido de carbono sigue aumentando en la rama de recesión del hidrograma y, como consecuencia, disminuye el índice de saturación de la rama de recesión del hidrograma. Se interpreta que estos resultados son debidos a la infiltración dispersa a través de suelos enriquecidos en dióxido de carbono que retrasan el flujo rápido desde la recarga en los sumideros hasta su afloramiento en los manantiales. Los hidrogramas en manantiales kársticos reflejan no sólo la mezcla cambiante del flujo de base y el de tormenta, sino también el cambio en el origen del agua de recarga durante el curso de la tormenta.

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Résumé Lenregistrement en continu du débit, de la conductivité et de la température de leau a été réalisé au cours dune série de crues à deux sources émergeant de calcaires, à Fort Campbell (Kentucky occidental, Tennessee, États-Unis). Des échantillons deau, prélevés à de courts pas de temps lors de ces crues, ont été analysés pour le calcium, le magnésium, les bicarbonates, le carbone organique total et le pH. Les chimiogrammes de calcium, dindice de saturation de la calcite et de la pression partielle en CO₂ ont été superposés aux hydrogrammes de crue. La concentration en calcium et la conductivité de leau se suivent bien et passent par un minimum correspondant au pic de lhydrogramme ou légèrement retardé. La pression partielle en CO₂ continue de croître au cours de la récession de lhydrogramme de même que lindice de saturation de la calcite décroît. Ces résultats sont interprétés comme étant dus à linfiltration dispersée au travers de sols riches en CO₂, décalée par rapport à larrivée de lécoulement rapide provenant de la recharge, à partir dune perte, de lécoulement de crue vers les sources. Les hydrogrammes de sources karstiques ne reflètent pas seulement le mélange variable de lécoulement de base et de lécoulement de crue, mais également un changement dorigine de leau de la recharge au cours de lépisode de crue.

     

Tracing dissolved O2 and dissolved inorganic carbon stable isotope dynamics in the Nyack aquifer: Middle Fork Flathead River, Montana, USA

The geochemistry and microbiology of shallow groundwater aquifers is greatly influenced by the concentration of dissolved oxygen gas (DO); however, the mechanisms that consume DO in groundwater (e.g., biotic or abiotic) are often ambiguous. The use of stable isotopes of molecular O₂ (δ¹⁸O-DO), in conjunction with stable isotopes of dissolved inorganic carbon (δ¹³C-DIC), has potential to discriminate between the various mechanisms causing DO depletion in subsurface waters.Here we report the results of spatial and seasonal changes in δ¹⁸O-DO and δ¹³C-DIC at the Nyack floodplain aquifer along the Middle Fork of the Flathead River near West Glacier, Montana, USA. Over a short, well constrained flow path (∼100 m) near a main recharge zone of the floodplain, the δ¹⁸O-DO consistently increased as DO concentrations decreased with distance from the recharge source. Concurrently, DIC concentrations increased and δ¹³C-DIC values decreased. These observations are explained by community respiration coupled with dissolution of calcite from cobbles in the aquifer matrix. When these results are compared to data from wells distributed over the entire floodplain (several km) a much less predictable relationship was observed between DO concentration and δ¹⁸O-DO. Many wells with low DO concentrations (e.g., <125 μmol L⁻¹ or 4 mg L⁻¹) had anomalously low δ¹⁸O-DO values (e.g., <20‰). Mass balance calculations show that approximately equal amounts of O₂ may be contributed to the aquifer by diffusion from the vadose zone and by advection from the river recharge. Calculations presented here suggest that diffusion across a narrow air-water interface can contribute isotopically light δ¹⁸O-DO to the saturated zone. Possible contributions of light δ¹⁸O-DO from other processes, such as isotopic exchange and radial oxygen loss from plant roots in or near the water table, are compared and evaluated.     

Precipitation and mixing properties of the “disordered” (Mn,Ca)CO3 solid solution

The enthalpy of mixing of the calcite-rhodochrosite (Ca,Mn)CO₃ solid solution was determined at 25 °C from calorimetric measurements of the enthalpy of precipitation of solids with different compositions. A detailed study of the broadening of powder X-ray diffraction peaks shows that most of the precipitates are compositionally homogeneous. All the experimental enthalpy of mixing (ΔH^m) values are positive and fit reasonably well (R² = 0.86) to a Guggenheim function of three terms:

     

鄂尔多斯盆地东缘大宁–吉县地区山西组山2 3亚段海陆过渡相页岩岩相与沉积环境变化

鄂尔多斯盆地东缘大宁–吉县地区二叠系山西组山₂ 3亚段海陆过渡相页岩是未来非常规油气勘探的重点目标,通过野外露头观察、岩心描述、薄片鉴定,结合全岩衍射、特征微量元素测试等手段,划分出硅质页岩相、硅质黏土质页岩相、钙质硅质(或硅质钙质)页岩相、黏土质页岩相4种页岩岩相类型。岩石学特征、地球化学指标表明,山₂ 3亚段继承了太原组沉积晚期地形平缓的陆表海格局,大规模海侵导致本区在山₂ 3沉积早期快速演化为海湾环境,沉积环境由氧化转为还原,水体盐度接近正常海水,有机质保存有利,形成了该亚段下部富有机质页岩相,其中钙质硅质(或硅质钙质)页岩相是相对优质的富有机质页岩岩相,具有高有机质含量、高脆性矿物含量、低黏土含量的特点,为页岩气开发有利层段。进入山₂ 3沉积晚期,区内逐渐演化为障壁岛沉积体系,在潟湖、滨岸沼泽环境中发育硅质黏土质页岩相、黏土质页岩相,虽多次受海侵影响,但海水影响程度总体上逐渐减弱,水体盐度呈降低趋势,沉积环境趋于氧化,有机质的保存条件变差,导致有机质含量总体偏低,同时脆性矿物含量偏少,不利于勘探开发。      

Patterns of Ca/Sr and Sr/Sr variation before and after a whole watershed CaSiO3 addition at the Hubbard Brook Experimental Forest, USA

Forty-one metric tons of the mineral wollastonite (CaSiO₃) was applied to an 11.8 hectare watershed at the Hubbard Brook Experimental Forest (HBEF; White Mountains, New Hampshire, USA) with the goal of restoring the Ca estimated to have been depleted from the soil exchange complex by acid deposition. This experiment provided an opportunity to gain qualitative information on whole watershed hydrologic flow paths by studying the response of stream water chemistry to the addition of Ca. Because the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of wollastonite strongly contrast that of other Ca sources in the watershed, the wollastonite-derived Ca can be identified and its amount estimated in various ecosystem components. Stream water chemistry at the HBEF varies seasonally due to shifts in the proportion of base flow and interflow. Prior to the wollastonite application, seasonal variations in ⁸⁷Sr/⁸⁶Sr ratios indicated that ⁸⁷Sr/⁸⁶Sr was higher during base flow than interflow, due largely to greater amounts of biotite weathering along deeper flow paths. After the application, Ca/Sr and ⁸⁷Sr/⁸⁶Sr changed markedly as the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr wollastonite dissolved and mixed with stream water. The Ca addition provided information on the response times of various flow paths and ion exchange processes to Ca addition in this small upland watershed. During the first year after the addition, wollastonite applied to the near stream zone dissolved and was partially immobilized by cation exchange sites in the hyporheic zone. In the second and third years after the addition we infer that much of this Ca and Sr was subsequently desorbed from the hyporheic zone and was exported from the watershed in stream flow. In the fourth through ninth years after the addition, Ca and Sr from wollastonite that had dissolved in upland soils was transported to the stream by interflow during wet periods when the ground water table was elevated. Between years three and nine the minimum annual Ca/Sr ratio (in late summer base flow) increased, providing evidence that Ca and Sr had increasingly infiltrated to the deepest flow paths. Strong seasonal variations in Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of stream water resulted from the wollastonite addition to upland forest soils, and these ratios have become sensitive to changing flow paths during the annual cycle. Most notably, high flow events now produce large excursions in stream geochemistry toward the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr ratios of wollastonite. Nine years after the application we estimate that ∼360 kg of Ca from wollastonite has been exported from the watershed in stream flow. The rate of export of Ca from wollastonite dissolution has stabilized at about 11 kg of Ca per year, which accounts for ∼30% of the dissolved Ca in the stream water. Given that 19 metric tons of Ca were applied to the watershed, and assuming this current rate of loss, it should take over 1000 years for this added Ca to be transported from the watershed.     

高密度井网区动静结合储层精细描述——以南堡凹陷高76断块Es31Ⅱ(1)小层为例

单砂体研究是高含水开发区中后期层内剩余油挖潜、改善开发效果的重要基础工作。笔者通过岩心观察,结合电测曲线特征,总结出研究区等高程、叠置砂体、沉积相变3种砂体对比模式及水下分流河道、河口坝、远沙坝3种砂体成因类型。最后结合动态注采对应关系进行单砂体展布规律分析。研究结果为注采调控提供地质依据,为精细注水示范工程的开展奠定基础,对揭示储层非均质性和预测剩余油分布都具有重要意义。     

Distribution of high field strength elements (Y, Zr, REE, Hf, Ta, Th, U) in adjacent magnetite and chert bands and in reference standards FeR-3 and FeR-4 from the Temagami iron-formation, Canada, and the redox level of the Neoarchean ocean

Adjacent magnetite and chert bands and reference standards FeR-3 and FeR-4 from the Neoarchean Temagami iron-formation (IF) show shale-normalized rare earth and yttrium (REY) patterns with low Nd/Yb ratios and positive Eu, Gd and Y anomalies, indicating that they formed as marine chemical sediments. In contrast to previous claims, none of the samples shows any Ce anomaly, indicating the absence of oxidative Ce-REY decoupling and arguing against oxic conditions in the wider vicinity of the Neoarchean “Temagami seabasin”. The distribution of Zr, Hf and Ta yields Zr/Hf and Hf/Ta ratios that differ from those of chondrites, average upper continental crust and local shales, suggesting that the Temagami IF is the only case observed so far in which a significant fraction of these elements is non-detrital but sourced from seawater. If Neoarchean seawater was characterized by Zr/Hf and Hf/Ta ratios similar to those of modern seawater these ratios point towards preferential scavenging of Hf over Zr and Ta, as is typical of the modern ocean. Similar to the 2.9 Ga old Mozaan IF in the Pongola Supergroup, South Africa, the Temagami IF shows low Th/U ratios that differ from those of the respective local shales and from that of average upper continental crust. Decoupling of U and Th results from U⁴⁺ oxidation in the Earth's surface system and fractionated Th/U ratios in these marine chemical sediments are, therefore, at odds with the lack of Ce anomalies. This suggests a different redox-sensitivity of the two paleo-redox-proxies Th–U and Ce-REY and demonstrates that the Temagami IF and the Mozaan IF warrant further study of other paleo-redox-proxies.     

In search of the mixed derivative ?2 M /? P ? T ( M = G , K ): joint analysis of ultrasonic data for polycrystalline pyrope from gas- and solid-medium apparatus

Elastic wave velocities for dense (99.8% of theoretical density) isotropic polycrystalline specimens of synthetic pyrope (Mg₃Al₂Si₃O₁₂) were measured to 1,000 K at 300 MPa by the phase comparison method of ultrasonic interferometry in an internally heated gas-medium apparatus. The temperature derivatives of the elastic moduli [(∂Ks/∂T) _P = −19.3(4); (∂G/∂T) _P = −10.4(2) MPa K⁻¹] measured in this study are consistent with previous acoustic measurements on both synthetic polycrystalline pyrope in a DIA-type cubic anvil apparatus (Gwanmesia et al. in Phys Earth Planet Inter 155:179–190, 2006) and on a natural single crystal by the rectangular parallelepiped resonance (RPR; Suzuki and Anderson in J Phys Earth 31:125–138, 1983) method but |(∂Ks/∂T) _P | is significantly larger than from a Brillouin spectroscopy study of single-crystal pyrope (Sinogeikin and Bass in Phys Earth Planet Inter 203:549–555, 2002). Alternative approaches to the retrieval of mixed derivatives of the elastic moduli from joint analysis of data from this study and from the solid-medium data of Gwanmesia et al. in Phys Earth Planet Inter 155:179–190 (2006) yield ∂² G/∂P∂T = [0.07(12), 0.20(14)] × 10⁻³ K⁻¹ and ∂² K _S /∂P∂T = [−0.20(24), 0.22(26)] × 10⁻³ K⁻¹, both of order 10⁻⁴ K⁻¹ and not significantly different from zero. More robust inference of the mixed derivatives will require solid-medium acoustic measurements of precision significantly better than 1%.