Use of 234U and 238U isotopes to evaluate contamination of near-surface groundwater with uranium-mill effluent: a case study in south-central Colorado, U.S.A.

The ²³⁴U/²³⁸U alpha activity ratio (AR) was determined in 47 samples of variably uraniferous groundwater from the vicinity of a uranium mill near Cañon City, Colorado. The results illustrate that uranium isotopes can be used to determine the distribution of uranium contamination in groundwater and to indicate processes such as mixing and chemical precipitation that affect uranium concentrations. Highly to moderately contaminated groundwater samples collected from the mill site and land immediately downgradient from the mill site contain more than 100?μg/l of dissolved uranium and typically have AR values in the narrow range of 1.0–1.06. Other samples from the shallow alluvial aquifer farther downgradient from the mill contain 10–100?μg/l uranium and plot along a broad trend of increasing AR (1.06–1.46) with decreasing uranium concentration. The results are consistent with mixing of liquid mill waste (AR≈1.0) with alluvial groundwater of small, but variable, uranium concentrations and AR of 1.3–1.5. In the alluvial aquifer, the spatial distribution of wells with AR values less than 1.3 is consistent with previous estimates of the probable distribution of contamination, based on water chemistry and hydrology. Wells more distant from the area of probable contamination have AR values that are consistently greater than 1.3 and are indicative of little or no contamination. The methodology of this study can be extended usefully to similar sites of uranium mining, milling, or processing provided that local geohydrologic settings promote uranium mobility and that introduced uranium contamination is isotopically distinct from that of local groundwater.     

Preferential solution of234U from recoil tracks and234U/238U radioactive disequilibrium in natural waters

A mathematical model to calculate the²³⁴U/²³⁸U activity ratio (AR) in an aqueous phase in contact with rock/soil is presented. The model relies on the supply of²³⁸U by dissolution and that of²³⁴U by dissolution and preferential release from radiation damaged regions (recoil tracks). The model predicts that values of²³⁴U/²³⁸U AR>1 in the aqueous phase can be obtained only from weathering “virgin” surfaces. Thus, to account for the observed steady-state supply of²³⁴U excess to the oceans by the preferential leaching model, ‘virgin’ rock/soil surfaces would have to be continually exposed and weathered. The²³⁸U concentration and²³⁴U/²³⁸U AR in continental waters allow us to estimate the exposure rates of “virgin” rock/soil surfaces.     

234U238U and 230Th234U activity ratios in mineral phases of a lateritic weathered zone

A selective phase extraction procedure was developed for the identification of the significant phases of a typical deep soil profile sampled in the vicinity of the Ranger No. 1 uranium ore body, Alligator Rivers region, N.T., Australia. The significant phases were identified as amorphous iron oxide, crystalline iron oxide and a clay/quartz resistate. The distribution of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra between the phases was measured. The results indicated that the amorphous iron oxide phase is in adsorption/desorption equilibrium with the ground water. The crystalline iron oxide phase contains a chemical control, the kinetics of which are commensurate with or less than the half-life of ²³⁰Th (7.52 × 10⁴ y). The clay/quartz resistate is enriched in ²³⁸U descendants in such a way that they are not readily accessible to the ground water.     

Dissolved Uranium and 234U/238U in the Yamuna and the Chambal Rivers, India

Dissolved uranium concentration and ²³⁴U/²³⁸U activity ratio have been measured in two distinctly different Indian drainage systems: the Yamuna headwaters in the Himalaya and the Chambal river system in the plains to study the weathering and mobility of uranium in these watersheds. The dissolved uranium in the Chambal river system ranges from 0.2 to 1.74 μg L⁻¹ during September (tail end of monsoon), whereas in the Yamuna river system, its concentration varies from 0.1 to 3.18 μg L⁻¹ during October (post-monsoon) and from 0.09 to 3.61 μg L⁻¹ in June (summer). In the Yamuna main stream, uranium is highest at its source and decreases steadily along its course, from 3.18 μg L⁻¹ at Hanuman Chatti to 0.67 μg L⁻¹ at Batamandi, at the base of the Himalaya. This decrease results mainly from mixing of the Yamuna mainstream with its tributaries, which are lower in uranium. The high concentration of uranium at Hanuman Chatti is derived from weathering of the Higher Himalayan Crystalline series (HHC) and associated accessary minerals, which may include uranium-mineralised zones. The ²³⁴U/²³⁸U activity ratios in the samples from the Chambal watershed are in the range of 1.15±0.05 to 1.67±0.04; whereas in the Yamuna the ratios vary from 0.95±0.03 to 1.56±0.07, during post-monsoon and from 0.98±0.01 to 1.30±0.03, during summer. The relatively high ²³⁴U/²³⁸U activity ratios in the Yamuna system are in its tributaries from the lower reaches viz., the Amlawa, Aglar, Bata, Tons and the Giri. It is estimated that ~9×10³ and ~12 × 10³ kg of dissolved uranium are transported annually from the Yamuna at Batamandi and the Chambal at Udi, respectively. This corresponds to uranium weathering rates of 0.9 and 0.09 kg U km⁻² y⁻¹ in the basins of the Yamuna and the Chambal headwaters. This study confirms that uranium weathering rate in the Himalaya is far in excess (by about an order of magnitude) of the global average value of ~0.08 kg U km⁻² y⁻¹.     

A routine method for the determination of the 234U238U ratio in natural water

A simple method to determine the ${}^{234}\text{U}{}^{238}\text{U}$ ratio in water by α-spectrometry is presented. The thiocyanate complex of uranium is extracted from the water by anion exchange. After elution of the U from the resin it is further purified by extraction from nitrate medium into ether. The source for α-spectrometry is prepared by oxalate electrodeposition. The overall yield is 70%.     

我国西北地区盐湖中的铀234U/238U比值示踪研究

内蒙古二连盆地、鄂尔多斯盆地典型含铀碳酸型盐湖水、岩两相234U/238U综合分析表明,碳酸型盐湖铀来源于大气降水和潜水对盐湖盆地周围中生代到现代富铀沉积物的溶滤、浸出,具有快速、近源物质来源特点。盐湖卤水和对应沉积物234U/238U值一般为0.8～1.2,湖卤水和潜卤水（晶间卤水）-岩两相中的铀处于沉积平衡状态。早白垩世～上新世含膏盐地层对比研究证实了富铀岩层234U/238U值随铀含量增大而减小,并趋近于1。室内盐湖水蒸发模拟实验发现残余卤水、沉积物234U/238U具有随蒸发程度增大逐渐减小的变化特征。盐湖现代沉积物物相研究发现铀主要以碳酸铀酰和吸附形式赋存在富含有机物和碎屑成分的含盐粘土沉积中,铀在盐类晶体中含量极少,仅存在于封闭水和结晶水中。卤水和沉积物ARu值是盐湖铀源及铀含量水平的指示标志之一。     

234Th238U radioactive disequilibrium in the surface layer of the ocean

²³⁴Th produced from ²³⁸U within sea water was found to be in radioactive disequilibrium with respect to its progenitor nuclide ²³⁸U in the surface layer of the ocean. The median value for ${}^{234}\text{Th}{}^{238}\text{U}$ activity ratio is 0.80 in the upper 200 m layer. A box-model calculation gives a removal residence time of thorium of about 0.38 yr. This suggests that ²³⁴Th is scavenged from the surface layer by the uptake of thorium by biota.     

洞穴石笋初始234U/238U值变化的古气候记录意义

通过对我国西南地区3个洞穴9根大型石笋272个初始234U/238U数据的分析研究,发现石笋初始234U/238U值长尺度变化与海洋沉积SPECMAP曲线δ18O记录有一定的正相关关系,与北纬25°夏季太阳辐射能量变化曲线呈一定的负相关关系,石笋初始234U/238U值的变化在冰期时波动强烈,而在间冰期波动相对平缓,在间冰期和冰期(间冰阶和冰阶)转化阶段该值呈跳跃状态变化。末次冰期及全新世阶段石笋初始234U/238U变化记录了该时段内的BA暖期和YD突变冷事件;全新世8200 a BP、7200 a BP、5200 a BP、4200 a BP、2800 a BP、1400 a BP 发生的几次较强冷事件在石笋初始234U/238U值都有相应记录,并且和长尺度的变化规律一致,冷事件发生时石笋初始234U/238U值偏重,暖期偏轻。封闭系统形成的洞穴石笋初始234U/238U变化类似于同地区洞穴石笋的δ18O对气候变化的记录特征,在我国西南地区两者与夏季风变化的强弱呈现一种负相关的关系,洞穴石笋初始234U/238U值可以作为一个有用的古气候替代指标来研究古降水的变化。     

Spatial and temporal variability of 234U/238U activity ratios in the Shu River,Central Asia

This study presents the temporal and spatial variability of ²³⁴U/²³⁸U activity ratios in the Shu River and provides interpretation to explain the downstream changes of uranium and the ²³⁴U/²³⁸U activity ratios in the study area. The positive linear correlation (R ² = 0.98, p < 0.001) between uranium concentration and specific electrical conductance is consistent with rock weathering and leaching as the major contributor of dissolved uranium in the studied area of the river. The ²³⁴U/²³⁸U activity ratio ranged between ~1.6 in the upper reaches of the river to ~1.15 furthest downstream. Activity ratios at specific sampling points do not show significant seasonal variability.     

Extreme fractionation of 234U238U and 230Th234U in spring waters,sediments, and fossils at the Pomme de Terre Valley,southwestern Missouri

Isotopic fractionation as great as 1600% exists between ²³⁴U and ²³⁸U in spring waters, sediments, and fossils in the Pomme de Terre Valley, southwestern Missouri. The activity ratios of ${}^{234}\text{U}{}^{238}\text{U}$ in five springs range from 7.2 to 16 in water which has been discharged for at least the past 30,000 years. The anomalies in ${}^{234}\text{U}{}^{238}\text{U}$ ratio in deep water have potential usefulness in hydrologic investigations in southern Missouri. Clayey units overlying the spring bog sediments of Trolinger Spring are enriched in ²³⁰Th relative to their parent ²³⁴U by as much as 720%. The results indicate that both preferential displacement via alpha recoil ejection and the preferential emplacement via recoiling and physical entrapment are significant processes that are occurring in the geologic environment.     

A study of234U/238U ratios in groundwaters of Taiyuan area,Shanxi Province

Uranium contents and²³⁴U/²³⁸U ratios have been determined on 29 water samples from the Taiyuan area, Shanxi Province. The results show that the same artesian aquifer has similar uranium contents and²³⁴U/²³⁸U activity ratios, and the deeper aquifers have higher A. R. values but lower uranium contents. The A. R. values increase slightly towards groundwater flow in the artesian aquifers dominated by oxidizing ground waters. The Lancun Spring and the famous Jinci Spring belong to two different karst groundwater systems, i.e., the east and west karst groundwater systems. The recharge area of the Lancun Spring should cover the wide limestone outcrops of middle Ordovician in the northeast. The Ordovician fissure-karst ground water to the Jinci Spring is extensively mixed with fissure water in Carboniferous-Jurassic formations and seepage water from the Fenhe River.     

Fractionation factor of 238U and 235U isotopes in the process of hydrothermal pitchblende formation: A numerical estimate

Owing to the rapid increase in available data on the natural variations of the ²³⁸U/²³⁵U ratio, new isotopic geochemical mark of redox processes are beginning to emerge. In this connection, numerical estimates of the ²³⁸U and ²³⁵U fractionation factor (α(U^IV?U^VI)) accompanying the reduction U^VI → U^IV are needed. Such an estimate has been obtained for hydrothermal pitchblende formation based on results of high-precision (±0.06‰) measurements of the ²³⁸U/²³⁵U ratio in local microsamples of coarse spherulitic pitchblende from carbonate-pitchblende veins at the Oktyabr’sky deposit (Strel’tsovsky uranium ore field, eastern Transbaikal region). For this purpose, we used the formation temperature of hydrothermal pitchblende and a maximum estimate of the fractionation factor for ²³⁸U and ²³⁵U isotopes in the solution-solid phase system under normal (25°C) conditions (Murphy et al., 2014). The most probable isotopic fractionation factor accompanying pitchblende crystallization from hydrothermal solution at T = 320?250°C falls into the interval α(U^IV?U^VI) = 1.00020?1.00023.     

Iron and Pyritization in Wetland Soils of the Florida Coastal Everglades

We explored environmental factors influencing soil pyrite formation within different wetland regions of Everglades National Park. Within the Shark River Slough (SRS) region, soils had higher organic matter (62.65 ± 1.88 %) and lower bulk density (0.19 ± 0.01 g cm^?3) than soils within Taylor Slough (TS; 14.35 ± 0.82 % and 0.45 ± 0.01 g cm^?3, respectively), Panhandle (Ph; 15.82 ± 1.37 % and 0.34 ± 0.009 g cm^?3, respectively), and Florida Bay (FB; 5.63 ± 0.19 % and 0.73 ± 0.02 g cm^?3, respectively) regions. Total reactive sulfide and extractable iron (Fe) generally were greatest in soils from the SRS region, and the degree of pyritization (DOP) was higher in soils from both SRS (0.62 ± 0.02) and FB (0.52 ± 0.03) regions relative to TS and Ph regions (0.30 ± 0.02 and 0.31 ± 0.02, respectively). Each region, however, had different potential limits to pyrite formation, with SRS being Fe and sulfide limited and FB being Fe and organic matter limited. Due to the calcium-rich soils of TS and Ph regions, DOP was relatively suppressed. Annual water flow volume was positively correlated with soil DOP. Soil DOP also varied in relation to distance from water management features and soil percent organic matter. We demonstrate the potential use of soil DOP as a proxy for soil oxidation state, thereby facilitating comparisons of wetland soils under different flooding regimes, e.g., spatially or between wet years versus dry years. Despite its low total abundance, Fe plays an important role in sulfur dynamics and other biogeochemical cycles that characterize wetland soils of the Florida coastal Everglades.     

Deposition and early diagenesis of microbial mud in the Florida Everglades

Microbial carbonate mud in the modern (<4 kyr) palustrine environment of the Florida Everglades is surprisingly susceptible to early diagenetic alteration. The low‐Mg calcite crystals show an open, trellis‐like crystal structure that yields a high surface area to volume ratio. This textural complexity, likely to be a result of organic influence, leads to abundant reaction sites vulnerable to both dissolution and subsequent precipitation. Rapid degradation of organics is attributed to both aerobic and anaerobic metabolisms. Geochemical signatures suggest increased denitrification within the freshwater environment and increased sulphate reduction at the (slightly) brackish mangrove transition zone. A transition from a freshwater to brackish depositional environment is likely to follow the Holocene sea‐level transgression. The textural complexity in these microbial carbonates causes an unexpectedly low preservation potential of original textural and geochemical signatures, even in low‐Mg calcite. Given the potential for early diagenesis of palustrine and perhaps other microbial carbonates, they should be used cautiously as archives for palaeoenvironmental proxies.     

234U/238U evidence for local recharge and patterns of ground-water flow in the vicinity of Yucca Mountain,Nevada, USA

Uranium concentrations and ²³⁴U/²³⁸U ratios in saturated-zone and perched ground water were used to investigate hydrologic flow and downgradient dilution and dispersion in the vicinity of Yucca Mountain, a potential high-level radioactive waste disposal site. The U data were obtained by thermal ionization mass spectrometry on more than 280 samples from the Death Valley regional flow system. Large variations in both U concentrations (commonly 0.6–10 μg l⁻¹) and ²³⁴U/²³⁸U activity ratios (commonly 1.5–6) are present on both local and regional scales; however, ground water with ²³⁴U/²³⁸U activity ratios from 7 up to 8.06 is restricted largely to samples from Yucca Mountain. Data from ground water in the Tertiary volcanic and Quaternary alluvial aquifers at and adjacent to Yucca Mountain plot in 3 distinct fields of reciprocal U concentration versus ²³⁴U/²³⁸U activity ratio correlated to different geographic areas. Ground water to the west of Yucca Mountain has large U concentrations and moderate ²³⁴U/²³⁸U whereas ground water to the east in the Fortymile flow system has similar ²³⁴U/²³⁸U, but distinctly smaller U concentrations. Ground water beneath the central part of Yucca Mountain has intermediate U concentrations but distinctive ²³⁴U/²³⁸U activity ratios of about 7–8. Perched water from the lower part of the unsaturated zone at Yucca Mountain has similarly large values of ²³⁴U/²³⁸U. These U data imply that the Tertiary volcanic aquifer beneath the central part of Yucca Mountain is isolated from north-south regional flow. The similarity of ²³⁴U/²³⁸U in both saturated- and unsaturated-zone ground water at Yucca Mountain further indicates that saturated-zone ground water beneath Yucca Mountain is dominated by local recharge rather than regional flow. The distinctive ²³⁴U/²³⁸U signatures also provide a natural tracer of downgradient flow. Elevated ²³⁴U/²³⁸U in ground water from two water-supply wells east of Yucca Mountain are interpreted as the result of induced flow from 40 a of ground-water withdrawal. Elevated ²³⁴U/²³⁸U in a borehole south of Yucca Mountain is interpreted as evidence that natural downgradient flow is more likely to follow southerly paths in the structurally anisotropic Tertiary volcanic aquifer where it becomes diluted by regional flow in the Fortymile system.     

Scavenging and particle residence times determined from 234Th/238U disequilibria in the coastal waters of Mecklenburg Bay

Activities of the naturally occurring radionuclide ²³⁴Th were determined in water samples of Mecklenburg Bay (SW Baltic Sea) using a new Th-specific diatomite adsorption technique followed by liquid scintillation spectrometry. Activities of “dissolved” (operationally defined as Th in the centrifugate) and particulate ²³⁴Th varied in the range of 1.4–6.9 and 0.9–9.3 mBq l⁻¹, respectively. A significant correlation between K_d and SPM concentration was found. From this particle-concentration effect, the “colloidal pumping” model predicts that 98% of the “dissolved” Th is associated with colloids rather than being truly dissolved. Relative to calculated activities of the parent nuclide ²³⁸U in the Bay, the ²³⁴Th data yielded mean ²³⁴Th scavenging residence times in the range of 1.2–9.7 days. Particulate ²³⁴Th activities are inversely correlated to SPM concentrations. Particle residence times ranged from a few days in winter up to 20 days in spring characterized by less intense bottom currents. The hydrodynamic regime is the master variable controlling scavenging of Th and other similarly particle-reactive elements in Mecklenburg Bay.     

Uranium isotopes (234U/238U) in rivers of the Yukon Basin (Alaska and Canada) as an aid in identifying water sources, with implications for monitoring hydrologic change in arctic regions

The ability to detect hydrologic variation in large arctic river systems is of major importance in understanding and predicting effects of climate change in high-latitude environments. Monitoring uranium isotopes (²³⁴U and ²³⁸U) in river water of the Yukon River Basin of Alaska and northwestern Canada (2001?C2005) has enhanced the ability to identify water sources to rivers, as well as detect flow changes that have occurred over the 5-year study. Uranium isotopic data for the Yukon River and major tributaries (the Porcupine and Tanana rivers) identify several sources that contribute to river flow, including: deep groundwater, seasonally frozen river-valley alluvium groundwater, and high-elevation glacial melt water. The main-stem Yukon River exhibits patterns of uranium isotopic variation at several locations that reflect input from ice melt and shallow groundwater in the spring, as well as a multi-year pattern of increased variability in timing and relative amount of water supplied from higher elevations within the basin. Results of this study demonstrate both the utility of uranium isotopes in revealing sources of water in large river systems and of incorporating uranium isotope analysis in long-term monitoring of arctic river systems that attempt to assess the effects of climate change.     

应用铀同位素研究砂岩型铀矿中的若干问题探讨

笔者通过对512铀矿床含矿层岩石中铀同位素分布特征的研究,对砂岩型铀矿床铀同位素组成的分区进行了讨论。根据不同氧化还原分带中样品铀同位素组分的分布特征,对Osmond铀钍同位素组成分区模式提出了补充修改意见,认为A区应定名为“地球化学（氧化还原）矛盾区”更宜。该砂岩型铀矿床的铀同位素组成分区特征不仅是预测铀矿化定位的依据,而且也充分说明了铀富集成矿过程的滚动性。     

Natural or fertilizer-derived uranium in irrigation drainage: a case study in southeastern Colorado,U.S.A.

Drainage from heavily cultivated soils may be contaminated with U that is leached from the soil or added as a trace constituent of PO₄-based commercial fertilizer. The effect of decades-long application of U-rich fertilizer on the U concentration of irrigation drainage was investigated in a small (14.2 km²) drainage basin in southeastern Colorado. The basin was chosen because previous reports indicated locally anomalous concentrations of dissolved NO₃ (6–36 mg 1⁻¹) and dissolved U (61 pg 1⁻¹) at the mouth of the only stream. Results of this study indicated minimal impact of fertilizer-U compared to natural U leached from the local soils. Detailed sampling of the stream along a 6 mile (9.7 km) reach through heavily cultivated lands indicated marked decoupling of the buildup of dissolved NO₃ and U. Dissolved U increased markedly in the upstream half of the reach and correlated positively with increases in Na, Mg, SO₄, B and Li derived from leaching of surrounding shaley soils. In contrast, major increases in dissolved NO₃ occurred farther downstream where stream water was heavily impacted by ground water return from extensively fertilized fields. Nitrogen isotopic measurements confirmed that dissolved NO₃ originated from fertilizer and soil organic N (crop waste). Uranium isotopic measurements of variably uraniferous waters showed little evidence of contamination with fertilizer-derived U of isotopically distinct²³⁴U/²³⁸U alpha activity ratio (A.R. = 1.0). Leaching experiments using local alkaline soil, irrigation water and U-rich fertilizer confirmed the ready leachability of soil-bound U and the comparative immobility of U added with liquid fertilizer. Relatively insoluble precipitates containing CaPU were formed by mixing liquid fertilizer with water containing abundant dissolved Ca. In the local soils soluble Ca is provided by dissolution of abundant gypsum. Similar studies are needed elsewhere because the mobility of fertilizer-derived U is dependent on fertilizer type, porewater chemistry and soil properties (pH, moisture, mineralogy, texture).     

Controls on herbaceous litter decomposition in the estuarine ecotones of the Florida Everglades

The effects of nutrient availability and litter quality on litter decomposition were measured in two oligotrophic phosphorus (P)-limited Florida Everglades esturies, United States. The two estuaries differ, in that one (Shark River estuary) is directly connected to the Gulf of Mexico and receives marine P, while the other (Taylor Slough estuary) does not receive marine P because Florida Bay separates it from the Gulf of Mexico. Decomposition of three macrophytes.Cladium jamaicense, Eleochaaris spp., andJuncus roemerianus, was studied using a litter bag technique over 18 mo. Litter was exposed to three treatments: soil surface+macroinvertebrates (=macro), soil surface without macroinvertebrates (=wet), and above the soil and water (=aerial). The third treatment replicated the decomposition of standing dead leaves. Decomposition rates showed that litter exposed to the wet and macro treatments decomposed significantly faster than the aerial treatment, where atmospheric deposition was the only source of nutrients. Macroinvertebrates had no influence on litter decompostion rates.C. jamaicense decomposed faster at sites, with higher P, andEleocharis spp. decomposed significantly faster at sites with higher nitrogen (N). Initial tissue C:N and C:P molar ratios revealed that the nutrient quality of litter of bothEleocharis spp. andJ. roemerianus was higher thanC. jamaicense, but onlyEleocharis spp. decomposed faster thanC. jamaicense. C. jamaicense litter tended to immobilize P, whileEleocharis spp. litter showed net remineralization of N and P. A comparison with other estuarine and wetland systems revealed the dependence of litter decomposition on nutrient availability and litter quality. The results from this experiment suggest that Everglades restoration may have an important effect on key ecosystem processes in the estuarine ecotone of this landscape.