喀斯特河流溶解态稀土元素组成变化及其控制因素

以化学萃取- 反萃取分离法为手段,结合等离子质谱分析仪测量了喀斯特地区乌江、沅江两大水系的枯水期河流的溶解态稀土元素含量。该两河流的化学组成代表了流经碳酸盐岩地层的河水的化学组成。与世界其它地区低pH的河水不同,喀斯特地区河水溶解态稀土元素含量较低,页岩标准化配分模式并不平坦,轻、重稀土元素分异因河流的不同而不同,乌江水系上游轻稀土元素( LREE)相对重稀土元素( HREE)富集,中下游HREE相对于LREE富集,沅江水系河水HREE相对于LREE富集,页岩标准化配分模式具明显的Ce、Eu负异常。乌江、沅江及其支流有高的溶解盐,含有较高的溶质浓度,河水水化学(高碱度、高离子含量、高pH值)和水/粒相互作用控制了喀斯特河水中溶解态稀土元素的含量和轻、重稀土元素的分异。      

巢湖的稀土元素地球化学特征

采用液-液萃取法和ICP-MS测试技术对巢湖的溶解态稀土元素进行了分析。结果表明,巢湖的溶解态稀土的含量与世界淡水相当,丰水期的样品含量高于其他季节。pH值和悬浮物、胶体是控制巢湖水体中溶解态稀土含量的主要因素。巢湖的溶解态稀土的分布模式以平坦型为主,少数呈现重稀土富集。丰水期和枯水期的溶解态稀土的(La/Yb)N值从西半湖区到东半湖区呈现有规律性的逐渐增大,并且丰水期的(La/Yb)N值低于枯水期。在富营养化湖泊中,胶体和水生生物可能是造成这一现象的主要原因。     

中国东部主要河流稀土元素地球化学特征

在2007年底至2008年初的枯水期间,系统采集了中国东部流域面积和径流量较大的33条河流沉积物、悬浮颗粒物和水样,采用等离子质谱法、X荧光光谱法等方法测定了14种稀土元素含量以及常量组分和水体pH值等理化指标。研究发现中国河流稀土元素浓度总体高于世界均值,且南方河流沉积物、悬浮物稀土元素含量高于北方河流,南方河流悬浮物态中稀土、重稀土呈现一定程度的相对富集,与我国上地壳稀土丰度和稀土矿产种类的南北分异相吻合。展示了以中国东部泥质岩稀土元素丰度标准化后的稀土配分模式及Ce、Eu异常特征,发现河流沉积物的中、重稀土元素相对富集,悬浮物轻稀土相对富集,溶解相重稀土富集的特征;北方河流溶解相稀土元素浓度明显大于南方河流,且除小清河外,溶解相Eu不同于沉积物与悬浮物而呈强烈的正异常,主要与河水理化性质影响下的稀土分异有关。研究发现小清河等少数河流沉积物中稀土元素为异常高值,经Al标准化处理、计算拟合剩余值后,认为小清河等河流稀土元素已受人为污染的影响。     

琼中麻粒岩的成因:稀土元素地球化学制约

稀土元素地球化学分析表明,琼中麻粒岩可以分为"高Ti"麻粒岩(TiO2含量大于1.0%)和"低Ti"麻粒岩(TiO2含量低于1.0%)两种化学类型."高Ti"麻粒岩以稀土总量高,轻稀土高度富集,轻、重稀土强烈分馏为特征,稀土配分曲线呈右倾单斜型,与本区变基性火山岩的稀土分布特征相似;低"Ti"麻粒岩以稀土总量较低,轻稀土分馏强烈,但重稀土分馏不明显为特征,稀土配分曲线呈重稀土平坦的左高右低型,与许多浅成基性岩的稀土分布特征相似;认为琼中麻粒岩形成于晋宁期的可能性最大.两类麻粒岩的识别,有利于深化对琼中杂岩形成和演化过程的认识.     

渤海湾盆地石炭二叠系稀土元素特征及其地质意义

采集了渤海湾盆地周缘露头剖面和盆内钻井岩心的泥岩及少量灰岩样品,采用电感耦合等离子质谱技术对样品进行了系统的稀土元素测试分析。测试样品稀土总量平均值为290.39 μg/g ,明显大于北美页岩组合样。各样品δEu为0.42~0.83,平均0.67,中度Eu负异常;大多样品Ce含量正常,δCe为0.51~1.22,平均0.97。稀土元素配分模式总体为轻稀土富集、重稀土亏损型,轻稀土段曲线明显“右倾”,重稀土段则较为“平坦”。灰岩及部分泥岩中Ce的负异常指示了晚石炭世本区陆表海的沉积环境特点,古海水为氧化环境。根据稀土元素的Eu异常及总的元素组合特点,判断渤海湾盆地石炭—二叠系沉积物主要来自盆地北缘的阴山古陆,母岩类型为花岗岩。     

东菲律宾海新型铁锰结壳中元素的赋存状态

为了解东菲律宾海新型铁锰结壳中元素的赋存状态, 采用化学提取方法对3个结壳样品进行了物相分析.不同类型结壳中成矿和稀土元素的赋存状态总体一致, 表明它们形成于相近的地质和海洋环境中.成矿元素中的Fe和Cu绝大部分赋存在残渣态中, Mn、Co和Ni则主要赋存在锰氧化物结合态、有机结合态和残渣态中, 并且埋藏型结壳样品锰氧化物结合态中赋存了相对更高比例的成矿元素.三价稀土元素主要集中在锰氧化物结合态中.两个沉积物表层结壳样品中的Ce主要集中在残渣态中.而埋藏型结壳样品中的Ce则主要赋存在锰氧化物结合态中, 这可能与该样品此相态中赋存了相对较多的Mn有关.呈碳酸盐结合态和有机结合态的稀土元素含量仅各占稀土总量的1%左右, 表明两者对结壳中稀土元素的富集作用很小.      

河流稀土元素地球化学研究进展

河流系统中,稀土元素(REE)受区域地质背景、风化作用、溶液化学以及水与颗粒物相互作用等因素的影响发生分异。河流悬浮物显示轻稀土(LREE)适度富集;河水显示重稀土(HREE)富集,或在HREE富集的基础上又有适度的中稀土(MREE)富集;与其它微量元素相比,REE在河水与颗粒物之间有较小的分配系数(K≈10-6);河流沉积物多显示平坦的REE配分模式。     

鄂尔多斯盆地盐56井长7段泥页岩稀土元素地球化学特征分析

鄂尔多斯盆地三叠系延长组长7段发育优质烃源岩,通过对盆地西部盐56井长7段泥页岩系统取样及稀土元素室内测试分析,结果表明：盐56井长71、长72、长73段稀土元素总量较高,均明显高于北美页岩,∑LREE/∑HREE、LaN/YbN比值显示轻重稀土分异明显,REE配分模式为明显的轻稀土富集、重稀土平坦及显著 Eu负异常右倾形态。根据REE配分模式,表明长7段泥页岩物源来自上地壳岩石;根据长7段各小层较高 REE总量及Ceanom均大于-0.1,显示长7段沉积期气候温暖湿润且水体为还原环境,且长73沉积期气候更为湿润,水体还原性更强。     

湘江悬浮物的稀土元素地球化学研究

在湘江及其支流采集了44件悬浮物样品进行稀土元素 ICP—MS分析。研究表明,湘江悬浮物中稀土总量(∑REE)、轻稀土(LREE) 和重稀土(HREE)含量分别为63～387 μg/g,58.2～353 μg/g和4.8～34μg/g。尽管湘江悬浮物中稀土分布不均匀,稀土含量相差很大,所有样品的球粒陨石标准化曲线均呈向右倾斜的富LREE的模式,北美页岩标准化模式为LREE稍富集的平坦型。湘江中下游河心与两岸水体悬浮物中稀土发生了明显分异。湘江悬浮颗粒物中REE受多方面因素控制,其源区控制了REE分配模式,而其稀土元素含量与颗粒中粘土矿物及重矿物有关。支流捞刀河悬浮物稀土的分布模式为Eu正异常型,与北美页岩有显著差别,捞刀河的悬浮物物源及成因有待进一步研究。     

贵州道坨锰矿菱锰矿的稀土元素特征

贵州道坨锰矿是2010年发现的一个大型碳酸锰矿床,含矿层位为南华系大塘坡组底部的含锰黑色页岩,主要含锰矿物为菱锰矿。通过对锰矿石全岩与提取出的菱锰矿进行稀土元素对比分析发现:(1)不同Mn含量的锰矿石的∑REE在(171.84~243.08)×10-6之间,提取的菱锰矿的∑REE在(32.52~135.69)×10-6之间,菱锰矿的∑REE占全岩∑REE的比例从15%到80%不等。菱锰矿的∑REE随着锰含量的升高而升高,且稀土元素配分模式都呈轻稀土含量少,中稀土富集,重稀土相对中稀土减少的"帽"式配分模式,而全岩的配分模式基本是平坦的直线型。随着全岩中Mn含量的升高,全岩和菱锰矿的配分模式越来越相似;(2)菱锰矿的δCe值在1左右,且随着Mn含量的升高。δCe值变大,这可能是因为Ce在锰氧化物或氢氧化物逐渐沉积富集的过程中,逐渐地被吸附,而造成了异常值的逐渐增大,说明菱锰矿的形成经过了锰氧化物或氢氧化物的阶段;(3)分别比较菱锰矿中Mn和P与轻、中、重稀土的相关性,Mn与中稀土的相关性最差,而P与中稀土的相关性最好。因此菱锰矿所表现出的中稀土富集的现象可能是其中的磷酸盐引起的,而磷酸盐与菱锰矿的共存可能是因为当时环境中磷与锰的分离不彻底造成的。     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).     

北京市街道灰尘中重金属元素赋存状态及环境效应

采用Tessier的五步提取法,对北京北西—南东剖面所采集的街道灰尘样品粒度≤100μm组分中As、Cd、Cr、Hg、Pb和Zn等6元素的5个形态(可交换态、碳酸盐结合态、铁锰氧化物结合态、有机物结合态、残渣态)的分布特征研究发现,在可交换态和碳酸盐结合态中Cd的含量比都为最高,Pb、Hg、Zn和As在有机物结合态中含量比相近,铁锰氧化物结合态中Pb所占比例最高,而As和Cr主要存在于残渣态中。6种街道灰尘污染元素的相对活动性和潜在生物利用度顺序为:Cd>Zn>Pb>Cr>Hg>As。     

电感耦合等离子体质谱法测定砂岩型铀矿样品中分步提取的铀

本文研究地质样品中铀形态的分析方法及应用技术,以进一步说明铀形态分析在地球化学找矿中的重要作用。该方法参考Tessier流程,将样品中的铀分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和结晶态,分别提取,提取溶液用高分辨率电感耦合等离子体质谱仪进行测量。设计的形态提取配方具有良好的可选择性和可重复性,经过国家标准物质、国际形态标准物质和人工模拟样品验证,证明形态提取试剂配方适合所定义的形态分析。通过对实际样品(总量铀为635μg/g)验证表明,碳酸盐结合态铀提取结果的可重复性最好(RSD为2.6%),其次为硫化物及有机物结合态铀(RSD为4.0%)、结晶态铀(RSD为6.0%)和铁锰氧化物结合态铀(RSD为6.1%),可交换离子态铀提取结果的可重复性最差(RSD为26%)。碳酸盐结合态铀与结晶态铀之比,可以用于反映地下铀矿的存在概率。     

Trace Metal Speciation of USGS Reference Sample MAG-I

The USGS reference sample marine mud MAG-1 has been subjected to a sequential extraction procedure designed to partition the constituent trace metals into five fractions: I-exchangeable; II- bound to carbonates; III-bound to Fe-Mn oxides; IV- bound to organic matter; V- residual. The analytical approach involved successive chemical extractions and the subsequent determination of trace metal concentrations (Co, Cu, Ni, Pb, Zn; Fe, Mn) in the leachates by atomic absorption spectrophotometry. The chemical speciation results obtained on four replicate sub-samples demonstrate that the coefficients of variation for metal concentrations in the individual fractions are generally better than + 10%. Comparison with published values for total trace metal concentrations in the MAG-1 sample suggests that the overall accuracy of the chemical extraction procedure is satisfactory.     

新疆某地浸砂岩型铀矿中铀赋存形态的研究

以新疆某地浸砂岩型铀矿为研究对象,参考Tessier逐级化学提取方法,对10件矿芯试样进行铀赋存形态的研究。将铀赋存形态分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和残渣态,其中前4种形态铀为活性铀,残渣态铀为惰性铀。研究结果显示,无论是试样间还是同一试样内,铀的形态分布特征都存在明显的差异。各形态铀的含量(平均值)占总量铀的比例为:残渣态(37.75%,RSD为1.80%)>碳酸盐结合态(20.56%,RSD为2.72%)>可交换离子态(15.51%,RSD为1.85%)>硫化物及有机物结合态(14.26%,RSD为2.08%)>铁锰氧化物结合态(11.91%,RSD为1.75%),表明残渣态铀是砂岩型铀矿石中铀的重要赋存形式。针对目前酸法地浸工艺,活性铀是可被浸出的部分,而惰性铀对资源回收是无效的,对于残渣态铀所占比例较高的铀矿石,铀的浸出值较低,在地浸过程中依靠提高溶浸剂的酸度和增加氧化剂对提高浸出率是无益的。     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。     

铜陵矿区水系沉积物中重金属存在形态特征研究

通过对铜陵水系沉积物重金属形态分析实验,研究了重金属各种形态在沉积物中分布特征。分析结果显示,矿区水系沉积物中Cu、Pb、Zn、Cd等重金属含量都显著的高于对照样品,水系已经受到重金属的污染。提出了防治和改善铜陵地表水环境污染的措施。