青海察尔汗盐湖别勒滩区段杂卤石成因及其成钾指示意义

别勒滩区段位于青海察尔汗盐湖西部,前人认为察尔汗盐湖固体钾盐矿物以光卤石为主,在别勒滩区段西部发现有杂卤石,但并未引起足够重视,对杂卤石成因未做详细研究。本文通过对别勒区段七个钻孔样品的矿物鉴定及地球化学分析,发现别勒滩区段杂卤石以原生和准同生交代方式赋存,且以后者为主,多交代石膏等硫酸盐矿物产出,少量出现交代石盐现象。杂卤石主要分布于别勒滩中西部地区,整个别勒滩区段自西向东出现了以杂卤石为主渐变为以钾石盐—光卤石为主的分布规律。结合别勒滩区段晶间卤水的补给条件,研究认为别勒滩区段杂卤石形成是涩聂湖硫酸镁亚型湖水与先期形成的盐类矿物发生交代反应的结果。别勒滩地区杂卤石作为典型的陆相成因,对研究海相蒸发岩矿床中普遍存在的杂卤石成因具有一定的对比借鉴意义,海相蒸发岩矿床中的杂卤石可能是盆地形成的内陆盐湖湖水与早期沉积的盐类矿物发生交代反应形成,对寻找海相钾盐有一定的指示意义。     

四川南充盐盆下中三叠统杂卤石形成条件及找钾意义

杂卤石(K₂SO₄·MgSO₄·2CaSO₄·2H₂O)是一种复盐,为盐类矿产中分布较为广泛的一种含钾矿物,在四川盆地三叠纪蒸发岩中广泛发育,并经常和其它钾镁盐矿物密切共生。由于杂卤石较其它钾镁盐矿物的溶解度低,易于残存保留,因此常被作为寻找钾盐矿床的重要标志和线索。其中南充盐盆嘉陵江组五段-雷口坡组一段(T₁j⁵-T₂l¹)的杂卤石分布面积最广,剖面揭露较完整,主要和纹层状硬石膏及菱镁矿、岩盐、“绿豆岩”等岩类共生,组成各种韵律层,根据岩矿鉴定、化学分析杂卤石还往往伴有微量的硫镁矾、无水钾镁矾等钾镁盐矿物。因此研究四川盆地三叠纪杂卤石分布特征、形成条件,对进一步寻找钾盐和指出找钾方向具有重要实际意义。     

青海察尔汗盐湖别勒滩区段固体钾盐液化前后物质组成对比及意义

察尔汗盐湖钾矿是中国最大的钾盐矿床,别勒滩位于察尔汗盐湖的最西端,目前正通过液化技术在别勒滩区段的固体钾盐层中提取钾资源。文章通过野外钻孔采集样品和室内系统的岩矿鉴定、X射线衍射、扫描电镜和化学成分分析,研究了含钾地层液化前、后的石盐和主要钾盐矿物的特征,对常量、微量元素进行了测定。得出的结论是：液化前和液化后主要钾盐矿物都是钾石盐、光卤石和杂卤石,其中杂卤石为最主要的钾盐矿物;液化前和液化后,富集程度高的微量元素为I、B和Li,可见别勒滩区段伴生元素I、B和Li具有开采潜力。通过计算得知此区段埋深22.42 m以上液化前w(KCl)平均为2.15%,液化后w(KCl)平均为1.68%,计算预测溶出的KCl资源量约为5 374万吨;埋深4.1 m以上液化前w(KCl)平均为2.23%,液化后w(KCl)平均为1.71%,计算预测溶出的KCl资源量约为1 087万吨,证明了液化法开采别勒滩地区固体钾盐经济可行。     

察尔汗盐湖别勒滩区段固态锂的赋存状态与分布特征

察尔汗盐湖别勒滩区段赋存大量具有开发潜力的固态锂资源,但目前对固态锂的赋存状态和分布特征研究较少。文章利用水溶法、稀酸溶法和全岩溶解法3种方法对该区4个钻孔的15件岩芯样品进行主微量元素分析。研究结果显示,水溶法的w(Li)(Li溶出量,余同)为23.37×10^-6～85.98×10^-6,稀酸溶法的w(Li)为47.77×10^-6～139.58×10^-6,全岩溶解法w(Li)为49.47×10^-6～151.64×10^-6。以同一样品全岩溶解所得的w(Li)为100%,水溶法、稀酸溶法的w(Li)平均值分别为56.44%和92.83%。结合矿物薄片鉴定、扫描电镜分析和X射线衍射的鉴定结果,岩芯样品中的矿物主要是石盐、杂卤石、光卤石、石英、绿泥石、钠长石、硬石膏、白云石、伊利石、菱镁矿和方解石等,推测固态锂大部分赋存于易溶盐类矿物,其余赋存于不易溶的碳酸盐、硫酸盐和硅酸盐等矿物中。根据4个钻孔岩芯样品的Li溶出量来看,察尔汗盐湖别勒滩区段固体钾盐层中固态锂的分...     

Na+,K+,Mg2+,Ca2+//Cl-,SO42——H2O六元体系中杂卤石形成条件的再认识

研究海水体系(即Na⁺,K⁺,Mg²⁺,Ca²⁺∥Cl^-,$SO_{4}^{2-}$-H₂O六元体系)中杂卤石的形成条件不仅有助于理解海相蒸发盐成因,对开发杂卤石钾资源利用技术也具有重要的指导作用。但杂卤石以及其他含有硫酸钙矿物(如二水石膏、半水石膏、无水石膏、钾石膏、多钙钾石膏、钙芒硝和水钙芒硝)的相平衡,无论是在实验研究方面还是在热力学模拟方面都仍然存在很多争议。由于缺乏杂卤石在复杂水溶液体系中可靠的相平衡数据,使人们对认识杂卤石成因和利用杂卤石钾资源带来巨大障碍。本工作对海水体系中杂卤石的形成条件进行了热力学模拟和实验研究。超过一年的长时间固液平衡实验表明25 ℃下Na⁺,K⁺,Mg²⁺,Ca²⁺∥Cl^-,$SO_{4}^{2-}$-H₂O六元体系中杂卤石的形成区域极为可观,且较前人实验结果均大数倍;同时证实了热力学模型预测结果的可靠性。这些结果为讨论盐矿床中杂卤石的形成条件提供了物理化学依据。25 ℃下可靠的热力学信息表明:杂卤石与其他盐类矿物的共生情况丰富多样,并且与前人看法不同,杂卤石的形成并不需要极高的钾、镁浓度。这给以杂卤石为指示寻找可溶性固体钾盐带来了挑战,但却指示了以杂卤石为线索更容易找到钾、镁盐未饱和的富钾卤水。     

川东北嘉陵江组嘉四-五段杂卤石地震识别及属性预测方法

杂卤石作为一种重要的钾盐矿产,在川东北地区下三叠统嘉陵江组嘉四-五段(T₁j^4-5)分布广泛,而T₁j^4-5埋藏深,杂卤石横向分布不稳定,利用地震技术对杂卤石进行预测是本区钾盐勘探的必要需求。而杂卤石夹杂在低速盐膏岩和高速膏云岩互层的地层中,一般单层较薄,在地震剖面上反应弱,地震识别困难。本文通过井震联合对比和地震正演分析,总结了杂卤石的地震响应特征,认为杂卤石由于形成机理的特殊性,其一般位于厚层盐膏层的上部,因此在地震上具有低频、强波谷背景上的高频、弱振幅的特征。在低频地震剖面上,杂卤石对应低频、强波谷的部位;而在高频地震剖面上,杂卤石对应高频、弱波峰的部位。在此基础上,通过分析传统的层属性在杂卤石预测上的难点和制约因素,提出了利用杂卤石在高、低频地震体上的幅频差异特征,通过体属性运算预测杂卤石分布的技术方法,并取得了较好的预测效果。该方法可为其他地区杂卤石的地震识别和预测提供借鉴。研究结果认为,杂卤石在纵向上主要发育于T₁j^4-5第2旋回盐膏层的上部,平面上主要在盐膏层塑性变形增厚的部位富集,呈条带状展布。     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.     

青海察尔汗盐湖固体钾盐物质组成及意义

察尔汗盐湖为我国目前最大的钾肥产地。根据钾盐层的矿物组成可以确定钾盐开发的难易程度以及化学组成可以确定钾盐富集层位并可对资源量进行估计的原则,通过在察尔汗盐湖别勒滩区段和察尔汗区段野外系统取样和室内的分析测试,研究了固体钾盐层的矿物组成、化学组成和物理参数。结果表明,别勒滩区段钾盐层最主要的钾盐矿物是杂卤石,其矿物晶形完好,排列紧密,表明液化开发至"中期阶段"即可利用,此段22.42 m以上钾盐的资源量约为2.5亿吨,主要赋存层位为断续的5段;察尔汗区段钾盐层最主要的钾盐矿物为光卤石,其矿物晶体排列疏松,表明液化开发到"晚期阶段"才可利用,察尔汗盐湖3区段3.55 m以上资源量共约为0.89亿吨,钾盐的主要赋存层位为浅表的60 cm以浅的盐层。对该区段钾盐的物理参数进行探讨,为察尔汗盐湖的进一步研究和固体钾盐的开发提供了新资料。     

青海别勒滩干盐湖石盐流体包裹体均一温度分析及地质环境意义

别勒滩位于察尔汗盐湖的最西端,最主要的沉积物为石盐,钾盐矿物主要为杂卤石、光卤石和钾石盐。文章研究了别勒滩区段盐类矿物形成的温度,为确定钾盐的形成条件提供了参考依据。别勒滩地区石盐流体包裹体均一温度呈现出3个或2个温度区段,即低温区段、中温区段和高温区段。低温区段均一温度变化范围为19.5～49.3℃,反映了大多数石盐结晶析出的卤水温度。中温区段均一温度变化范围为50.1～99.3℃,与盐湖底部卤水所达到的最高温度相对应。高温区段均一温度变化范围为100.3～195.6℃,可能为太阳池事件的响应。由太阳池下部对流层中沉积的盐类矿物组合或相关参数计算的古温度只能为其形成时的卤水温度,不能代表当时的气温。在同一样品中,既出现高温流体包裹体,又出现中温或低温流体包裹体,是矿物生长经历太阳池下部对流层环境与中部非对流层环境所致。别勒滩地区在18 m以上部位可能出现6次太阳池事件,它们的位置 （编号）分别为0.40～1.00 m（S₆）、1.70～2.90 m（S₅）、7.90～8.10 m（S₄）、9.90～10.10 m（S₃）、10.80～11.00 m（S₂）、16.39～16.63 m（S₁）。其中第6次太阳池事件（S₆）可能是1989年发生的大水灾在盐湖沉积中的体现。     

新疆博阿断裂附近地表水和地下水的水化学和同位素特征及水质评价

新疆地区属于西北干旱地区,水资源紧缺,为了研究其地下水的水文地球化学特征及水质情况,在博阿断裂附近采集与收集温泉水、地表水和冷泉水共15个样品,进行了水化学和氢氧同位素特征分析,并进行了水质评价。结果表明,研究区地表水的水化学类型主要为SO₄-Na、Cl·SO₄-Na和HCO₃·SO₄-Ca·Na型。温泉水的水化学类型为SO₄·HCO₃-Na/HCO₃·SO₄-Na和HCO₃·Cl-Na型。冷泉水的水化学类型为SO₄·HCO₃-Mg·Ca、HCO₃-Ca、HCO₃-Mg·Ca和SO₄·HCO₃-Ca型。研究区冷泉水中Mg²⁺、Ca²⁺、HCO₃^-的主要来源是白云石、方解石和石...     

Formation and chemical evolution of magnesium chloride brines by evaporite dissolution processes—Implications for evaporite geochemistry

The evolution of magnesium chloride brines with high bromide contents via a multistage reaction and dissolution process has been studied in brine seeps of a German potash mine. The observed chemical trends and phase equilibria can be modeled and interpreted in terms of a NaCl solution (cap rock brine) infiltrating into a potash zone characterized by the metamorphic mineral assemblage kieserite + sylvite + halite + anhydrite. Establishment of a persistent, stable equilibrium assemblage and constant fluid composition in the invariant point IP1 of the six component (Na-K-Mg-Ca-Cl-SO₄-H₂O) system of oceanic salts is prevented by the perpetually renewed input of NaCl-brine and by the intermittent exposure of incompatible kieserite. Instead, the solutions develop towards the metastable invariant point IP1(gy), with the mineral assemblage carnallite + polyhalite + sylvite + halite + gypsum, where gypsum takes the place of anhydrite (stage I). The temporary exposure of kieserite and the ensuing formation of polyhalite effectively buffer the solutions along the metastable polyhalite phase boundary during stages II and III. Eventually, in stage IV, polyhalite becomes depleted and admixture of more NaCl brine leads to low sulfate solution compositions, which are now only constrained by carnallite + sylvite + halite, and the once hexary system degenerates to a quaternary one (Na-K-Mg-Cl-H₂O) in point E. Bromide in brines shows equilibrium partitioning with respect to the wall rock minerals. The pattern of evolving brine compositions may serve as a model for similar brine occurrences, which in some cases may have been misinterpreted as remains of fossil, highly concentrated and chemically modified seawater. Similar magnesium chloride brines of salt lakes (e.g., Dead Sea, Dabusun Lake) show subtle differences and are constrained by fewer mineral equilibria (more degrees of freedom), and their low sulfate contents are due to gypsum precipitation, driven by calcium chloride input from dolomitization reactions. Finally, the observed reaction sequence is generalized, and a model for the formation of magnesium sulfate depleted, chloride-type potash salts and bischofite deposits by leaching of sulfate-type evaporites is proposed.     

Potassium-argon dating of polyhalite in southeastern New Mexico

Polyhalite, K₂Ca₂Mg (SO₄)₄-2H₂O, is an important mineral in many evaporites. Although its use for K-Ar dating has never been investigated, our results indicate that it is a very useful mineral for dating events ranging from the time of potash mineralization to any younger events which may have affected the evaporite. Five K-Ar dates on pure polyhalite, including two from included material and from beds distorted by the formation of a rubble chimney, yield dates between 198 and 216 Myp, in good agreement with Rb-Sr dates and the diagenetic age of the potash deposits from the same rocks. Two polyhalites mixed with sylvite gave lower dates (154 and 174 Myr) which is to be expected because of radiogenic ⁴⁰Ar loss from the sylvite phase. One polyhalite, formed after the intrusion of a 31 Myr lamprophyre dike, yielded 21 Myr. Collectively our results indicate that pure polyhalite is satisfactory for K-Ar dating and may provide critical age information in studies of the geologic history of the evaporite sequences.     

Sediment characteristics and mineralogy of salt mounds linked to underground spring activity in the Lop Nor playa,Western China

Salt mounds are commonly distributed along playa margins and typically comprise alternating layers of loose fine sand and slightly hard halite-rich sediments as a result of long-term underground spring activity. A model of salt mound development was constructed for this study. It suggests that wind-blown sand supply and upward recharge of underground springs are two important factors in salt mound construction. Furthermore, it proposes that salt mound height is mainly controlled by the vertical transport range of underground springs and the thickness of the capillary fringe. A 1.5 m representative profile dug from the center of salt mound LP1 in the Lop Nor playa revealed a fairly complicated mineral assemblage including halite, gypsum, anhydrite, glauberite, epsomite, anhydrite, calcite, bischofite, polyhalite, schoenite, kieserite and carnallite. This matches closely with the assemblage predicted by the EQL/EVP model. The groundwater in the area is highly concentrated brine rich in Cl⁻ and Na⁺ and poor in Ca²⁺, displaying low alkalinity, and containing considerable amounts of SO₄²⁻, Mg²⁺ and K⁺. Chemical analysis of groundwater revealed considerable variation in the salinity and chemical composition of groundwater over time. The Cs-137 technique was used to measure the accumulated ages of the salt mounds. This method may prove useful in the research of relatively young playa environments where carbon dating techniques are unworkable because of an absence of carbon-rich materials in recent saline sediments.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

川东盆地长寿地区三叠系杂卤石的发现及其成因研究

笔者先后2次对川东盆地盐矿实地考察,并系统采集了样品。水溶化学分析结果表明,长寿地区T1j4-2地层中岩盐w(K+)较高,最高可达3.25%,明显高于其他盐矿点(合川盐矿、云阳盐矿及万州高峰盐矿)。岩盐Br-含量也较高;Br×103/Cl值相对较高,一般为0.26~0.36,最大可达0.41,已达到晚期石盐沉积,甚至是钾镁盐早期沉积阶段。而后又对K+含量较高的样品(不含KCl)进行配矿分析,同时结合岩矿鉴定及XRD分析验证,首次发现和确定长平3井的主要含钾矿物为杂卤石,样品中不含钾石盐(KCl)。通过对样品薄片镜下观察,杂卤石为自形-半自形的板状和柱状及叶片状形态,结合杂卤石与石盐的接触关系及Br×103/Cl值分析,认为长平3井杂卤石为原生沉积成因,而非如前人所认为的四川盆地其他地区的杂卤石成因——后期含钾镁较高的热卤水交代硬石膏而形成。这一认识对该区寻找可溶性钾盐具有一定的启示作用。     

青海別勒滩试验区低品位固体钾盐液化开采的野外实验研究

我国是一个钾盐资源贫乏的国家,长期依靠进口。在我国,钾盐找矿难度较大,经过50多年的勘查,盐湖找钾已很难有新的大突破。但值得注意的是,在察尔汗盐湖、马海、罗布泊等地有数亿吨低品位固体钾盐,这些资源相当于一个超大型钾矿,对低品位固体钾盐的开发是缓解我国钾盐短缺重要的、可行的方向。本文在青海別勒滩试验区对3米以浅地层进行了野外溶矿实验,研究低品位固体钾盐固液转化过程中的水动力学和水化学变化等问题。研究发现,溶矿过程中试验区内不同时间、不同单元探坑中水位变化差别较大,表明別勒滩地区在地质结构、构造,特别是孔隙度等方面存在较大差异;溶矿过程中试验区内不同时间、不同单元探坑中卤水的KCl含量有差异,溶矿初期,探坑内卤水KCl含量变化与水位埋深呈相反趋势,水位抬升效果最好的区域其卤水品质较差;随着溶剂的不断补充和与固体钾矿反应时间的增加,卤水KCl含量整体趋于平均,但总体上含量较低。经过几个月的溶矿实验,探坑中卤水KCl含量仍较低,溶矿效果不理想。这可能是因为近几年对低品位固体钾盐持续开采,地层中钾盐矿物含量降低导致溶矿后卤水中KCl含量降低。因此,需要对浅部矿床地质特征进行精准评估,精细化分形溶采管理,以避免盲目补给溶剂,造成无效溶解,使得溶采工程低效率运行,生产成本提高。