地浸采铀矿山地下水环境修复研究进展

地浸采铀技术已成为世界采铀的主流工艺,采区退役后地下水环境修复亦为人们所关注的热点。文章简要介绍了碱法、中性和酸法三种典型地浸采铀技术的特点,系统分析了地浸采铀对地下水环境的影响,并以酸法地浸铀矿山地下水环境修复技术为例,重点介绍了物理化学修复技术和生物修复技术及其原理与应用,归纳总结了其优缺点,并对未来的研究方向进行了展望。指出下一步应加强在酸性与氧化环境中能使铀固定并长期稳定的新技术,高活性、强适应性修复菌群的选育、驯化技术,地下水异位-原位协同生物修复技术,以及放射性核素及重金属在铀矿地浸地下水环境中的吸附-解吸、氧化-还原、溶解-沉淀等行为与机理及其主控因素等方面的研究。     

The influence of irrigation and Wuliangsuhai Lake on groundwater quality in eastern Hetao Basin,Inner Mongolia,China

Geochemical and isotopic characterization of groundwater and lake-water samples were combined with water and total dissolved solids balances to evaluate sources of groundwater quality deterioration in eastern Hetao Basin, Inner Mongolia, China. Groundwater quality is poor; 11 of 13 wells exceed drinking-water guidelines for at least one health-based parameter and all wells exceed aesthetic guidelines. The well water is largely derived from Yellow River irrigation water. Notably high uranium concentrations in the Yellow River, relative to world rivers, suggest groundwater uranium and other trace elements may originate in the river-derived irrigation water. Complex hydrostratigraphy and spatial variation in groundwater recharge result in spatially complex groundwater flow and geochemistry. Evapotranspiration of irrigation water causes chloride concentration increases of up to two orders of magnitude in the basin, notably in shallow groundwater around Wuliangsuhai Lake. In addition to evapotranspiration, groundwater quality is affected by mineral precipitation and dissolution, silicate weathering, and redox processes. The lake-water and TDS balances suggest that a small amount of discharge to groundwater (but associated with very high solute concentrations) contributes to groundwater salinization in this region. Increasing salinity in the groundwater and Wuliangsuhai Lake will continue to deteriorate water quality unless irrigation management practices improve.     

Spatial and temporal variability of surface water and groundwater before and after the remediation of a Portuguese uranium mine area

The old Senhora das Fontes uranium mine, in central Portugal, consists of quartz veins which penetrated along fracture shear zones at the contact between graphite schist and orthogneiss. The mine was exploited underground until a depth of 90 m and was closed down in 1971. The ores from this mine and two others were treated in the mine area by the heap-leach process which ended in 1982. Seven dumps containing a total of about 33,800 m³ of material and partially covered by natural vegetation were left in the mine area. A remediation process took place from May 2010 to January 2011. The material deposited in dumps was relocated and covered with erosion resisting covers. Surface water and groundwater were collected in the wet season just before the remediation, in the following season at the beginning of the remediation and also after the remediation in the following dry season. Before, at the beginning and after the remediation, surface water and groundwater have an acid-to-alkaline pH, which decreased with the remediation, whereas Eh increased. In general, before the remediation, uranium concentration was up to 83 μg/L in surface water and up to 116 μg/L in groundwater, whereas at the beginning of the remediation it increases up to 183 μg/L and 272 μg/L in the former and the latter, respectively, due to the remobilization of mine dumps and pyrite and chalcopyrite exposures, responsible for the pH decrease. In general, after the remediation, the U concentration decreased significantly in surface water and groundwater at the north part of the mine area, but increased in both, particularly in the latter up to 774 μg/L in the south and southwest parts of this area, attributed to the remobilization of sulphides that caused mobilization of metals and arsenic which migrated to the groundwater flow. Uranium is adsorbed in clay minerals, but also in goethite as indicated by the geochemical modelling. After the remediation, the saturation indices of oxyhydroxides decrease as pH decreases. The remediation also caused decrease in Cd, Co, Cr, Ni, Pb, Zn, Cu, As, Sr and Mn concentrations of surface water and groundwater, particularly in the north part of the mine area, which is supported by the speciation modelling that shows the decrease of most dissolved bivalent species. However, in general, after the remediation, Th, Cd, Al, Li, Pb, Sr and As concentrations increased in groundwater and surface water at south and southwest of the mine area. Before and after the remediation, surface water and groundwater are contaminated in U, Cd, Cr, Al, Mn, Ni, Pb, Cu and As. Remediation caused only some improvement at north of the mine area, because at south and southwest part, after the remediation, the groundwater is more contaminated than before the remediation.     

砂岩含水介质中铀的吸附和迁移行为研究

地浸铀矿山退役后,含水层中残留的含铀浸出液随着地下水的运动向下游迁移扩散,存在对周边地下水污染的风险。本文设计了若干组批实验和柱实验,研究铀在北方某地浸铀矿山砂岩含水介质中的吸附和迁移行为。实验结果表明,砂岩对铀的吸附在12 h以内达到平衡,铀初始浓度越高,砂岩的铀吸附容量越大;砂岩对铀的吸附为吸热反应,温度升高有利于吸附反应的进行。溶液pH值和共存 {\mathrm{HCO}}_3^{-}浓度会对铀的吸附作用产生强烈的影响:pH值在7左右时,铀的吸附量最高; {\mathrm{HCO}}_3^{-}浓度越高,铀的吸附量越低。这些影响是通过改变溶液中铀的络合形态和砂岩矿物表面的电荷性质实现的。柱实验表明,pH值、铀浓度、流速和 {\mathrm{HCO}}_3^{-}浓度是影响铀在饱和砂岩含水介质中迁移的重要因素。pH值≤7时,pH值越高,砂岩柱越不易被铀穿透;而铀浓度、流速、 {\mathrm{HCO}}_3^{-}浓度越高,砂岩柱越易被铀穿透。两点非平衡模型可以很好地拟合不同条件下铀在砂岩柱中的迁移过程。批实验获得的分配系数是柱实验的1.16.6倍。通过对比实验条件、含水层特性和地下水化学特征,确定分配系数为48.1 mL/g时,较适合描述研究区内砂岩含水层中的铀迁移。上述认识为地浸铀矿山地下水铀的反应运移过程和天然自净化机理提供了理论依据。     

Concentration of uranium levels in groundwater

The uranium isotopes during their course of their disintegration decay into other radioactive elements and eventually decay into stable lead isotopes. The cause of environmental concern is the emanation of beta and gamma radiation during disintegration. The present study tends to estimate uranium in groundwater trapped in granite and gneiss rocks. Besides, the study aims at estimating the radiation during natural disintegration process. The water samples were collected and analyzed following inductively coupled plasma mass spectrometric technique while water sample collection was given to the regions of Kolar District, South India, due to the representation. The significant finding was the observation of very high levels of uranium in groundwater compared to similar assays reported at other nearby districts. Also, the levels were considerable to those compared to groundwater levels of uranium reported by other scientists. On the basis of this study, it was inferred that the origin of uranium was from granite strata and there was a trend of diffusion observed in the course of flow-path of water in the region.     

324铀矿床近地表矿体中长寿命铀系核素和类比微量元素迁移特征

对一近地表铀矿体中某些铀系长寿命核素的放射性平衡状态和１４种微量元素迁移特征研究得出，自该铀矿床６３Ｍａ前生成至今，仅近１Ｍａ来，当上覆花岗岩遭剥蚀使矿体近地表时，矿石中天然放射性核和微量元素才因水－岩反应沿围岩破碎带，裂隙发生迁移；裂隙两侧岩石受水－岩反应影响的范围较小，裂隙面的化学组分以溶失为主，裂隙两侧粘土化花岗岩中则以核素、元素的扩散和吸附为主，最后阐述了本研究结果对高放废物处置库安全评价     

REE/trace element characteristics of sandstone-type uranium deposits in the Ordos Basin

1 Introduction The Ordos Basin is the second largest sedimentary basin in China. During the last 10 years, a great progress has been achieved in the aspects of tectonic evolution, dynamics process, inner and outer geological processes during Mesozoic-Cen…     

砂岩型铀矿床中铀矿物的形成机理

本文通过对砂岩型铀矿床中铀在不同地球化学环境中的行为、存在形式及铀矿物种类的分析，论述了主要工业铀矿物——沥青铀矿的形成机理：(1)铀是变价元素，在氧化环境中活化迁移，在还原环境中还原沉淀；(2)来自于氧化环境的[UO2(CO3)3]^4-、[UO2(CO3)2]^2-在氧化还原过渡带与有机质、硫化物及低价铁等还原剂发生反应，形成铀的简单氧化物——沥青铀矿；(3)有机质、粘土矿物等吸附UO2^2 ，加快了其被还原的速度，有利于铀的富集。因此认为：有机质还原UO2^2 形成H2S和H2S还原UO2^2 的作用是沥青铀矿形成的主要原因，这一反应在中性和弱碱性碳酸盐溶液中广泛和普遍存在。H2S等还原剂的存在是环境Eh值下降的主要原因，从而使水中的UO2^2 在氧化还原过渡带处于过饱和状态，加速了铀的吸附和沉淀。     

Distribution of uranium in German bottled and tap water

The results presented in this paper on uranium in bottled and tap water were determined within the scope of the project “European Groundwater Geochemistry: Bottled Water” of the Geochemistry Expert Group of EuroGeoSurveys. The analyses of bottled water provide an inexpensive approach to obtain information about European groundwater geochemistry. For this study, the uranium concentrations in 1785 European mineral water samples were analyzed by ICP–QMS in the BGR laboratories. The dataset is used to obtain a first impression about natural concentration levels and variation of uranium in groundwater (and bottled water) at the German and European scale.     

An integrated approach for assessment of groundwater quality in and around uranium mineralized zone,Gogi region,Karnataka, India

Assessment of groundwater quality is an important aspect of water security, which is the key to ensure sustainable development. The objective of the study is to bring out an integrated approach for assessment of groundwater quality for drinking and irrigation purposes. Gogi region, Karnataka, India was chosen as the study area due to the effect of the presence of medium-grade uranium deposits. An integrated approach including the concentration of major ions, trace elements and uranium was employed to investigate the quality of groundwater. Totally, 367 groundwater samples were collected periodically from 52 wells distributes over the Gogi region and the parameters such as pH, electrical conductivity, total dissolved solids (TDS), Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^?, SO₄ ^2?, NO₃ ^?, Zn, Pb, Cu, and uranium of groundwater were analysed. Spatial distribution maps of various chemical constituents were prepared using geographic information system and its temporal variation was plotted in box and whisker plot. The analytical data were compared with Bureau of Indian Standards and World Health Organisation standards to determine drinking water quality and parameters such as salinity hazard, alkalinity hazard and percent sodium were estimated to assess the irrigation quality. Multivariate statistical analysis by cluster analysis was also performed which results in two groups consisting of wells with unsuitable water for drinking purposes. Groundwater in about 15% of the sampling wells were found to be unsuitable for domestic purpose based on TDS and about 17% were unsuitable based on uranium concentration. Finally, integration of spatial variation in TDS and uranium reveals that about 25% of the wells were unsuitable for domestic purposes. It is suggested that such an integrated approach needs to be formulated considering major ions, trace elements and radioactive elements for proper assessment of water quality. Implementation of managed aquifer recharge structures in the study area is suggested since it would potentially reduce the concentration of ions.     

铀矿地质钻探岩心样品系统分析法

铀矿地质钻探岩心样品系统分析法包括：岩心样品的γ辐射测量、切片观测测量、样品粉碎、矿物微粒分选、激光拉曼光谱分析、傅立叶红外光谱分析、包体流体观测与测量、X射线荧光光谱分析、X射线衍射分析、电子探针分析、高纯锗γ能谱分析、湿法化学分析、ICP～MS微量元素分析、铀矿物和其它矿物同位素组成分析等步骤,通过这些步骤的系统分析,得到铀矿地质钻探岩心样品的全息资料,为铀矿地质勘探提供支持和服务。     

地下水中酸性污染羽的自然净化作用数值模拟研究

酸法地浸采铀对铀矿层的地下水环境有极大的破坏作用,当开采结束后将形成酸性地下水污染羽。为恢复含矿含水层的水质,必须采取有效的污染治理措施。自然净化是一种较经济的方法,但是必须对其有效性进行评价。本研究以某退役地浸铀矿采区含矿含水层为研究对象,采用反应溶质运移模拟方法来研究酸性污染羽在含水层中的自然净化作用。研究中使用PHT3D模型模拟污染羽的运移,模拟反应组分共12种、沉淀溶解矿物共6种,模拟时长为5a。模拟结果表明:酸性污染物进入地下水后,形成了由方解石、Al(OH)3（a）和 Fe(OH)3（a）反应所控制的pH缓冲区;随着酸性污染羽的向下游高pH值地下水区域移动,方解石溶解与石膏沉淀反应可使SO42-浓度产生明显下降,其他主要金属离子污染物也有明显的自净作用。     

高分异花岗岩浆可能是华南花岗岩型铀矿床主要铀源——来自诸广山南体花岗岩锆石铀含量的证据

锆石的U-Pb测年、Hf和O同位素及稀土、微量元素的研究与应用已获得诸多进展,但锆石中铀含量所蕴藏的地质意义却较少被关注。华南花岗岩型铀矿床的铀源一直存在争议,不同观点认为其分别来自早期已固结地质体、分异岩浆、地幔柱或热点以及U、Th、K富集圈。为尝试利用锆石中的铀含量来追索铀源,本文通过搜集诸广山南体花岗岩锆石U-Pb同位素测年文献,掌握了该花岗岩中14个岩体、37件样品、3种岩性,共467个锆石定年数据。通过数据分析发现印支期(253Ma、244Ma)和燕山期(139Ma、124Ma)具高分异特征的4件酸性岩脉(小岩体)样品中锆石的铀含量明显高于同期岩体。依据铀矿床中高分异酸性岩脉(小岩体)侵位期、基性岩脉侵位期、铀成矿早期(140~90Ma)三者的良好对应关系,结合这一锆石铀含量指示,初步认为华南花岗岩型铀矿床中铀可能主要来自高分异花岗岩浆;推测花岗岩型铀成矿可能属壳幔混合作用结果,即铀源来自地壳分异岩浆,成矿流体和矿化剂主要来自地幔,而成矿空间受断裂系统控制。岩体锆石铀含量或可在铀源丰度、矿床品位判别等方面发挥积极作用。     

Relationships between radium and radon occurrence and hydrochemistry in fresh groundwater from fractured crystalline rocks, North Carolina (USA)

Naturally-occurring radionuclides (uranium, radium, and radon), major dissolved constituents, and trace elements were investigated in fresh groundwater in 117 wells in fractured crystalline rocks from the Piedmont region (North Carolina, USA). Chemical variations show a general transition between two water types: (1) slightly acidic (pH 5.0–6.0), oxic, low-total dissolved solids (TDS) waters, and (2) near neutral, oxic to anoxic, higher-TDS waters. The uranium, radium, and radon levels in groundwater associated with granite (Rolesville Granite) are systematically higher than other rock types (gneiss, metasedimentary, and metavolcanic rocks). Water chemistry plays a secondary role on radium and radon distributions as the ²²²Rn/²²⁶Ra activity ratio is correlated with redox-sensitive solutes such as dissolved oxygen and Mn concentrations, as well as overall dissolved solids content including major divalent cations and Ba. Since ²²⁴Ra/²²⁸Ra activity ratios in groundwater are close to 1, we suggest that mobilization of Ra and Rn is controlled by alpha recoil processes from parent nuclides on fracture surfaces, ruling out Ra sources from mineral dissolution or significant long-distance Ra transport. Alpha recoil is balanced by Ra adsorption that is influenced by redox conditions and/or ion concentrations, resulting in an approximately one order of magnitude decrease (~ 20,000 to ~ 2000) in the apparent Ra distribution coefficient between oxygen-saturated and anoxic conditions and also across the range of dissolved ion concentrations (up to ~ 7 mM). Thus, the U and Th content of rocks is the primary control on observed Ra and Rn activities in groundwater in fractured crystalline rocks, and in addition, linked dissolved solids concentrations and redox conditions impart a secondary control.     

Application of major and trace elements as well as boron isotopes for tracing hydrochemical processes: the case of Trifilia coastal karst aquifer,Greece

The Trifilia karst aquifer presents a complex hydrochemical character due to the intricate geochemical processes that take place in the area. Their discernment was achieved by using the chemical analyses of major, trace elements and boron isotopes. Major ion composition indicates mixing between seawater and freshwater is occurring. Five hydrochemical zones corresponding to five respective groundwater types were distinguished, in which the chemical composition of groundwater is influenced mainly due to the different salinization grade of the aquifer. The relatively increased temperature of the aquifer indicates the presence of hydrothermal waters. Boron isotopes and trace elements indicate that the intruding seawater has been hydrothermally altered, as it is shown by the δ¹¹B depleted signature and the increased concentrations of Li and Sr. Trace elements analyses showed that the groundwater is enriched in various metallic elements, which derive from the solid hydrocarbons (bitumens), contained in the carbonate sediments of the Tripolis zone. The concentration of these trace elements depends on the redox environment. Thus, in reductive conditions As, Mn, Co and NH₄ concentrations are high, in oxidized conditions the V, Se, Mo, Tl and U concentration increases while Ni is not redox sensitive and present high concentration in both environments.     

Geochemistry and hydrology of perched groundwater springs: assessing elevated uranium concentrations at Pigeon Spring relative to nearby Pigeon Mine,Arizona (USA)

The processes that affect water chemistry as the water flows from recharge areas through breccia-pipe uranium deposits in the Grand Canyon region of the southwestern United States are not well understood. Pigeon Spring had elevated uranium in 1982 (44 μg/L), compared to other perched springs (2.7–18 μg/L), prior to mining operations at the nearby Pigeon Mine. Perched groundwater springs in an area around the Pigeon Mine were sampled between 2009 and 2015 and compared with material from the Pigeon Mine to better understand the geochemistry and hydrology of the area. Two general groups of perched groundwater springs were identified from this study; one group is characterized by calcium sulfate type water, low uranium activity ratio ²³⁴U/²³⁸U (UAR) values, and a mixture of water with some component of modern water, and the other group by calcium-magnesium sulfate type water, higher UAR values, and radiocarbon ages indicating recharge on the order of several thousand years ago. Multivariate statistical principal components analysis of Pigeon Mine and spring samples indicate Cu, Pb, As, Mn, and Cd concentrations distinguished mining-related leachates from perched groundwater springs. The groundwater potentiometric surface indicates that perched groundwater at Pigeon Mine would likely flow toward the northwest away from Pigeon Spring. The geochemical analysis of the water, sediment and rock samples collected from the Snake Gulch area indicate that the elevated uranium at Pigeon Spring is likely related to a natural source of uranium upgradient from the spring and not likely related to the Pigeon Mine.     

Geochemical constraints on underground disposal of uranium mill tailings

A three phase investigation has been conducted on groundwater quality impacts of the underground disposal of tailings from acid-leach milling of uranium ores. These phases included field collection and analysis of samples obtained during backfilling of mill tailings in empty underground mine stopes, collection of soil samples from mill tailings piles and previously backfilled stopes, and evaluation of thermodynamic constraints on possible geochemical transformations. Contaminants of principal concern include As, Mo, Se, U, V and Ra-226.The investigation has shown that short-term degradation of groundwater due to backfill disposal of the sand fraction of uranium tailings is negligible. Long-term effects, defined as those occurring after mining operations cease and the mine fills with water, are predicted to also be very small. This is attributed to immobilization of pollutants through chemical reduction and precipitation, as well as adsorption onto aquifer materials. This conclusion is substantiated, in part, by observation of high concentrations of most of the contaminants on the silt and clay fraction of the soil samples collected, in contrast to the concentrations found on the sand fraction.     

Arsenic and uranium transport in sediments near abandoned uranium mines in Harding County,South Dakota

Sediment samples were analyzed as part of ongoing environmental investigations of historical U mining impacts within Custer National Forest in Harding County, South Dakota. Correlations between As and U content, grain size and soil mineralogy were determined to identify contaminant fate and transport mechanisms. Soil samples collected near the mining source zone and up to 61 km downgradient of the minesites were analyzed. Samples were homogenized and wet sieved through polymer screens, and metal(loid) concentrations were determined using inductively coupled plasma mass spectrometry (ICP-MS). Powder X-ray diffraction (XRD) analysis identified quartz as the primary mineral for all size fractions, with varying amounts of analcime, indicative of volcanic origin. Selected samples were examined for trace mineral composition using scanning electron microscopy (SEM). The presence of Fe sulfides and Fe (hydr)oxides indicate heterogeneity in redox potentials on a microscopic scale. Elevated metal(loid) concentrations were associated with trace concentrations of Fe sulfide, indicating an influence on metal transport during weathering. Sequential chemical extractions (SCE) performed on source sediment fractions demonstrated that most As and U was adsorbed to Fe- and Mn-oxides and carbonates with lesser amounts bound by ion exchange, organics and Fe sulfides. Large changes in U/Th and As/Th ratios were observed to coincide with geochemical changes in the watershed, suggesting that metal(loid)–Th ratios may be used in environmental investigations to identify geochemically-significant watershed conditions.     

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.