Rare earth element characteristics of the carboniferous Huanglong Formation dolomites in eastern Sichuan Basin,southwest China: Implications for origins of dolomitizing and diagenetic fluids

Marine dolostones of Carboniferous Huanglong Formation constitute major gas reservoir rocks in eastern Sichuan Basin. However, the investigation with respect to sources of dolomitizing and diagenetic fluids is relatively underexplored. The current study attempts to investigate the REE characteristics of dolomites using seawater normalization standard, and therefore discusses the origins of dolomitizing and diagenetic fluids, on the basis of continuous 47.33-m-long core samples from the second member of Huanglong Formation (C₂h₂) in eastern Sichuan Basin. Low Th, Sc, and Hf concentrations (0.791 × 10⁻⁶, 4.751 × 10⁻⁶, and 0.214 × 10⁻⁶, respectively), random correlation between total REE concentration (ΣREE) and Fe or Mn abundance, and seawater-like Y/Ho ratios (mean value of 45.612) indicate that the carbonate samples are valid for REE analysis. Based on petrographic characteristics, four dolomite types are identified, including micritic-sized dolomite (type Dol-1), fine-to medium-sized dolomite (type Dol-2), medium-to coarse-sized dolomite (type Dol-3), and coarse-to giant-sized saddle dolomite (type Dol-4). Dol-1 dolomites, characterized by positive Ce anomaly (mean value of 6.398), light REE (LREE) enrichment, and heavy REE (HREE) depletion with mean LREE/HREE ratio of 12.657, show micritic calcite-like REE patterns, indicating seawater origin of their dolomitizing fluids. Dol-1 dolomites were formed in sabkha environment whereas the dolomitizing fluids originated from evaporative brine water due to their micritic crystal sizes and tight lithology. Dol-2 dolomites, particularly subtype Dol-2a barely developing vuggy porosity, also show micritic calcite-like REE patterns, suggesting their dolomitizing fluids were seawater or seawater-derived fluids. This inference is confirmed by low Fe and Mn concentrations, which range from 651 μg/g to 1018 μg/g (mean value of 863 μg/g) and 65 μg/g to 167 μg/g (mean value of 105 μg/g), respectively, whereas homogenization temperatures (T_h, mean value of 103 °C) indicate that Dol-2 dolomites were formed under burial environment. Dol-3 dolomites, in form of cements of Dol-2 dolomites, show similar REE patterns to their host minerals (i.e., Dol-2 dolomites), indicating their parent source was possibly derived from Dol-2 dolomites. Dol-3 dolomites have high Fe and Mn concentrations with mean values of 3346 μg/g (ranging from 2897 μg/g to 3856 μg/g) and 236 μg/g (ranging from 178 μg/g to 287 μg/g), respectively, indicating the involvement of meteoric water. Meanwhile, it confirms that the dissolution in Dol-2 dolomites was caused by meteoric water leaching. Positive Eu anomalies (mean value of 1.406) in Dol-4 dolomites, coupled with high homogenization temperatures (mean value of 314 °C), suggest that Dol-4 dolomites precipitated from hydrothermal fluids. High Fe and Mn concentrations (mean values of 2521 μg/g and 193 μg/g, respectively) in Dol-4 dolomites likely results from interactions of hydrothermal fluids with deep burial clastic rocks.     

川南沐川地区宣威组底部铌-稀土多金属富集层富集规律、沉积环境与成矿模式

云南、贵州地区对晚二叠世宣威组底部Nb-REE多金属富集层的研究取得了重要进展,但其成因还有较大争议.为厘清沐川地区宣威组底部Nb-REE多金属富集层成因机制及富集规律,本研究开展了野外实地调查、矿物学、岩相古地理与岩石地球化学等系统性研究,探讨其物源、富集规律,建立了成矿模式.结果 表明,川南沐川地区宣威组底部Nb-...     

土壤重金属连续提取方法的优化

重金属在污染土壤中的形态分布决定着重金属的迁移性和危害的程度。土壤重金属形态分析应用最多的是Tessier和BCR连续提取法。Tessier和BCR连续提取法没有考虑土壤样品的特征。美国环保署危险废物浸出毒性鉴别标准法虽然考虑土壤pH值,但没有划分形态。采集不同pH土样,结合Tessier、BCR和毒性浸出鉴别方法的特征,优化出针对不同pH值土壤的连续提取方法,将土壤中重金属划分为活性态、次生碳酸盐结合态、次稳定态和稳定态。用优化的连续提取方法对土样进行连续提取,重金属回收率为85%~115%。优化连续提取方法的结果与Tessier和BCR结果对比显示优化连续提取方法克服了Tessier连续提取法对非石灰质土壤提取过量BCR连续提取法对石灰质土壤提取不足的缺点。优化后的连续提取方法数据稳定可靠,可作为重金属形态分析方法使用。     

Source speciation resolving hydrochemical complexity of coastal aquifers

There is a growing concern of seawater intrusion to freshwater aquifers due to groundwater overexploitation in the eastern coastal belt of Southern India. The problem becomes complex in the regions where industrial effluents are also contaminating the freshwater aquifers. In order to understand the hydrochemical complexity of the system, topographic elevation, static water level measurements, major ion chemistry, ionic cross plots, water type contours and factor analysis were applied for 144 groundwater samples of shallow and deep sources from Quaternary and Tertiary coastal aquifers, located within the industrial zone of 25 km² area near Cuddalore, Southern India. The ionic cross plots indicates dissolution of halite minerals from marine sources and seawater mixing into inland aquifers up to the level of 9.3%. The factor analysis explains three significant factors totaling 86.3% of cumulative sample variance which includes varying contribution from marine, industrial effluent and freshwater sources.     

贵州开阳白马洞铀矿化岩层地球化学特征

贵州开阳白马洞铀矿是重要的蚀变型铀矿,通过对白马洞清虚洞组黑色蚀变岩及白云岩风化红粘土和寒武系牛蹄塘组黑色页岩的常量元素、微量元素和稀土元素组成的分析研究,发现铀元素含量与Re、Se、Pb、Cu、As、Sb、Tl、Zn、Ni、Mo、Co、S含量为正相关关系,铀含量高,则Re、Se、Pb、Cu、As、Sb、Tl、Zn、Ni、Mo、Co、S含量也高,其中As、Co、Mo、Ni、Re、Tl、Zn、S具有显著的正相关性,而且地表土壤中Se、V、Mo 等元素的富集是铀矿找矿的主要标志之一。根据白马洞清虚洞组、寒武系牛蹄塘组黑色页岩、灯影组硅化白云岩的稀土元素配分模式分析,硒富集和铀矿化矿源层不仅是牛蹄塘组黑色页岩,可能有更深部的矿源存在。认为硒富集区是铀矿找矿远景区域;古代炼汞矿渣富集铀矿,值得开发利用和治理。     

河南小秦岭金矿稀土元素地球化学特征及地质意义

小秦岭金矿产于新太古界太华群变质岩中,其中的次级拆离断裂为赋矿构造。为了探究矿床的地球化学特征和矿床成因,从矿区主要地质体采集了100件来自太华群地层、文峪岩浆岩和矿石的样品进行测试,其稀土元素的主要特征为：太华岩群的ΣREE值为30.81×10^-6~188.66×10^-6;δEu值为0.62~1.24;花岗岩和脉岩类ΣREE值为58.22×10^-6~365.98×10^-6;δEu为0.90~1.10;矿石的ΣREE值多集中于76.74×10^-6~358.22×10^-6,δEu值多集中于0.74~1.14。结果表明：各地质体稀土总量接近,没有Eu异常或有微弱的正、负铕异常;矿石的稀土元素含量特征与太华群接近,而与文峪等花岗岩相差较远。分析认为,成矿物质主要来源于太华群地层而不是花岗岩。     

藏北羌塘盆地中央隆起带下二叠统展金组沉积岩稀土元素地球化学特征及其地质意义

对于青藏高原北部羌塘盆地中央隆起带晚古生代的构造演化历史,学术界目前仍存在不同观点。位于盆地中央隆起带角木日地区的羌资5井揭示出的下二叠统展金组细碎屑岩,对于该地区古地理研究和构造背景约束具有重要意义。通过对该井中17个展金组粉砂质泥岩和泥质粉砂岩样品的稀土元素地球化学研究表明:样品 ω(ΣREE) 整体较高,ω(ΣLREE)/ω(ΣHREE)及(La/Yb)_N等比值显示其具有较弱的轻、重稀土元素分异;Ce_anom,Ce/Ce^*,Eu/Eu^*等参数反映样品主要形成于具有一定深度的浅海还原环境;(La/Yb)_N值自下而上呈降低趋势,表明下部的沉积速率低于上部。稀土元素组合及其比值特征指示展金组物源以玄武岩和沉积岩混合为主。根据La-Th-Sc构造背景判别图解分析,并与不同构造背景下的杂砂岩稀土元素特征比较,认为展金组沉积岩的物源可能来自于具有类似岛弧构造特征的环境。     

塔里木盆地塔北隆起奥陶系-侏罗系泥岩稀土元素地球化学特征

分析了塔里木盆地塔北隆起奥陶系、三叠系和侏罗系泥岩的稀土元素丰度。不同时代泥岩都表现出轻稀土富集、重稀土含量均一和具有Eu负异常特征;但它们∑LREE/∑HREE、LaN/YbN、(La/Yb)UCC、Eu/Eu和Ce/Ce等参数则显示这些泥岩形成时的物源和环境有差别。奥陶纪时,研究区处于相对稳定的沉积环境,物源为成熟度高的大陆上地壳;二叠纪到三叠纪构造-火山活动强烈,部分沉积物来自火山岩的风化;侏罗纪塔北隆起区则进入稳定构造沉降阶段。这一差别对认识塔里木盆地及周边造山带形成演化研究有指示意义。     

ANC,BNC and mobilization of Cr from polluted sediments in function of pH changes

During the manufacturing of chromate salts (1972–1992) large quantities of Chromite Ore Processing Residue (COPR) were released into a decantation pond east of the former chemical plant of Porto-Romano (Durres, Albania), giving rise to yellow colored pond sediments. These Cr(VI) bearing sediments were deposited upon Quaternary silty-clay lagoonal sediments rich in iron oxides and organic matter. The pH values in these lagoonal sediments vary around 6.6, while in the pond sediments, it is mainly acidic (due to the presence of the sulfur stock piles in the area and the release of the H₂SO₄ from the activity of the former chemical plant), varying between 1.4 and 3.8. Continuous leaching of the COPR waste resulted in yellow-colored surface water runoff. The prediction of pH changes in the different types of sediments based upon acid/base neutralizing capacity (ANC/BNC) jointly with the quantitative data on release of heavy metals and especially Cr is considered an important advantage of the pH_stat leaching test if compared to conventional leaching procedures. Thus, factors controlling the leaching of Cr(VI), Cr(III), Ca, Al, Fe, Mg from the COPR were investigated by means of pH_stat batch leaching tests and mineralogical analysis. Moreover, mathematical and geochemical modeling complemented the study. The COPR in the area contain very high concentrations of chromium 24,409 mg/kg, which mainly occurs as Cr(III) (75–90%) as well as Cr(VI) (25–10%). The leaching of Cr(VI) occurs in all the range (2–10) of the tested pH values, however, it decreases under acidic conditions. Beside some reduction of Cr(VI) to Cr(III), the Cr(VI) content of the leachtes remains relatively high in the acidic environment, while the limning of Cr(VI) pond sediments will increase the release of the latter specie. The leaching of the Cr(III) occurs strictly under acidic conditions, whereby limning of these sediments will give rise to the lower solubility of Cr(III). The key mineral phases responsible for the fast release of the Cr(VI) are: the chromate salts (i.e. sodium chromate and sodium dichromate), while sparingly soluble chromatite (CaCrO₄) and hashemite (BaCrO₄) release Cr(VI) very slowly. Thus, pH and mineral solubility have been identified as key factors in the retention and the release of the hexavalent CrO₄ ²⁻ and Cr₂O₇ ⁻ from the COPR-rich pond sediments.     

Contamination,chemical speciation and vertical distribution of heavy metals in soils of an old and large industrial zone in Northeast China

Heavy metal pollution of soils has become a major concern in China as a consequence of rapid urbanization and industrialization in recent years. However, the evaluation on soil heavy metal pollution in Shenyang, the largest heavy industrial base city in China, has not yet been conducted. In this study, accumulation, chemical speciation, and vertical distribution Cu, Zn, Pb and Cd in soils were studied and pollution condition was assessed in Tiexi Industrial District of Shenyang, the largest and oldest industrial zone in Northeastern China. The results showed that in topsoil, the average concentration of total Cu, Zn, Pb, and Cd was 209.06, 599.92, 470.19 and 8.59 mg kg⁻¹, respectively, much higher than the national threshold limit. The values of pollution index and integrated pollution index showed that the pollution level was Cd > Cu > Zn > Pb, and Cd, Cu and Zn belong to heavy pollution level. The residual, Fe and Mn oxide-bound, and organic-bound species accounted for about 90%, while carbonate-bound and exchangeable species accounted for about 10%. This study indicates that the soils in the industrial zone were widely and extremely polluted by multi-heavy metals as a result of long-term industrial activities.