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1.
To investigate the distribution pattern and controlling factors of rare earth elements (REEs) in riverine sediments, river mouth sediments were collected at five geographically different rivers around the Yellow Sea. Two- (1 M HCl leached and residual fractions) and five-step sequential extraction schemes (the SEDEX method) were applied to size-separated sediments < 20 µm. For the total REE composition, patterns normalized relative to the upper continental crust (UCC) showed light REE (LREE) and middle (MREE) enrichments in the Korean river sediments and MREE enrichment in the Chinese river sediments. LREE and MREE enrichments in 1 M HCl leached fractions played a major role in the distribution patterns of the total compositions in all the river sediments. About half of LREE enrichment in Korean river sediments was explained by the residual fraction. Comparison of the REE composition with major elements (Al, Fe, Ca, P) in each fraction of the SEDEX scheme revealed that MREE enrichment could be explained by reactive iron minerals, including goethite and hematite, although REE/Fe ratios showed different trends among the rivers due to different major REE-host iron minerals. After extracting reactive irons, authigenic phosphate, and carbonate, the sequential 1 M HCl fraction indicated that LREE enrichment in Korean river sediments may have originated from clay minerals, such as chlorite. These observations suggest that LREE enrichment may be a good tracer, while MREE enrichment should be used cautiously considering diagenetic modification, when using the REE composition to identify the sources of terrestrial materials. 相似文献
2.
红壤中稀土元素结合形态的分布及分配 总被引：2，自引：0，他引：2
红壤剖面中稀土元素结合形态的分布研究表明,稀土元素的各种结合形态中以残渣态为主,其次为铁锰氧化物结合态,大部分稀土元素的可交换态、碳酸盐结合态、有机质结合态及酸溶态含量较为接近。稀土元素结合形态在剖面层中的分布大致可分为两类,一类以表层含量较高,如有机质结合态;另一类以深层含量较高,如可交换态、碳酸盐结合态、残渣态（大部分稀土元素表现为C层＞A层＞B层）和酸溶态（主要表现为C层＞B层＞A层）,而铁锰氧化物结合态变化较复杂,但主要集中在深层。不同母质对不同稀土元素各种结合形态的分布有一定的制约作用．表现为某些稀土元素的一些结合形态在一种或几种母质的红壤中占主导地位。稀土元素结合形态的分配研究表明,元素Pr、Tb、Tm、Yb、Lu的分异普遍比较显著,在不同结合形态中呈现富集或亏损,而Ce、Sm、Eu等元素则主要在某一种结合形态中发生分异。从稀土元素的各种结合形态与红壤的硅酸盐成分及其有机质含量、pH值间的相关分析认识到结合形态与红壤本身成分间的密切关系。 相似文献
3.
Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge,Indian Ocean
The rare earth element (REE) contents of sixteen surficial calcareous sediments from the southwestern Carlsberg Ridge, Indian
Ocean, have been determined. The total REE vary from 35 ppm to 126 ppm and are inversely related to the calcium carbonate
content. REEs show a strong positive correlation with Al + Fe + K + Mg + Na (r
2= 0.98) and Mn + Fe + Cu + Ni (r
2= 0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The
aeolian input into these sediments is suggested from the weak positive Eu/Eu* anomaly. Shale-normalized (NASC) pattern along
with La(n)/Yb(n) ratio suggest enrichment of heavy REE (HREE) relative to the light REE (LREE) with a negative Ce/Ce* anomaly implying retention
of a bottom water REE pattern.
An erratum to this article is available at . 相似文献
4.
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。 相似文献
5.
采用液-液萃取法,连续提取法和ICP-MS测试技术,对龙感湖不同季节水和颗粒物中稀土元素进行研究.结果表明,龙感湖的溶解态稀土含量极低,稀土总含量(ΣREE)在3.14～129.81ng/kg之间,且季节性变化明显.龙感湖溶解态稀土元素表现出平坦型的页岩配分模式,这是由于在草型湖泊中溶解态稀土主要以吸附在微细胶体上的形式存在,水粒相互作用在这个过程中起主要控制作用.悬浮物中的稀土含量顺序为:残渣态>>Fe-Mn结合态>>有机态和AEC态,颗粒物中稀土元素主要以残渣态形式存在.Fe-Mn结合态、有机态和AEC态的页岩配分模式为中稀土富集,残渣态的页岩配分模式为平坦型.这说明中稀土与轻重稀土相比具有更强的潜在地球化学活性,但在龙感湖的环境中的迁移能力相对轻重稀土来说较弱. 相似文献
6.
A. L. Ramanathan P. Vaithiyanathan V. Subramanian B. K. Das 《Estuaries and Coasts》1993,16(3):459-474
Major ion chemistry of water and elemental geochemistry of suspended and surficial sediments collected from the Cauvery Estuary were studied to understand the geochemical processes in this tropical estuarine system. Specific conductance (EC), total dissolved solids (TDS), and total suspended matter (TSM) increased conservatively with increasing chlorinity. In general, SO4 2?, Na, K, Ca, and Mg showed an increasing trend while H4SiO4 and PO4 3? showed a decreasing trend toward the sea. Additional removal mechanisms operating for these ions in the Cauvery Estuary have been identified based on observed concentrations. Factor analysis pointed out the sources contributing to the observed trends in estuarine water chemistry. POC and PON decreased toward the high chlorinity zone. TSM in the Cauvery Estuary were mostly of inorganic nature. Stable carbon isotope values showed that the carbon was equally of marine and terrestrial origin and helped to delineate the contribution of river water and seawater. The ? mean size (a logarithmic grain size scale commonly used by sedimentologists) indicated that the surficial sediments were primarily comprised of coarse and silt, whereas suspended sediments were principally silt and clay. Suspended sediments were enriched in clays compared to surficial sediments. Quartz and feldspar were abundant among detritals while chlorite, kaolinite, and montmorillonite were dominant among clays. Silicon was the most abundant element in the sediments followed by Al, Ca, Na, K, Fe, Mn, and P. Heavy metals were enriched in the suspended sediments compared to the surficial bottom sediments as follows: Fe = 3.5, Mn = 7.4, Pb = 1.1, Zn = 15.2, Cu = 7.4, and Cr = 4.0. The levels of Cd, Cr, Zn, and Fe increased up the middle reaches and then decreased toward the sea due to urban effluent and fertilizer input. Size fractionation studies indicated that the metal concentration in the finer fraction was 50% higher by mass than the coarse silt and fine silt fractions. Chemical fractionation studies showed that the abundance of metals were in the order of residual > organic/sulfide > carbonate > Fe/Mn oxide > exchangeable fractions. 相似文献
7.
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. 相似文献
8.
Ajay Kumar R. K. Singhal Sabyasachi Rout P. M. Ravi 《Environmental Earth Sciences》2013,70(7):3057-3066
The resulting concentration data sets of major (Na, K, Mg, Ca and Fe) and trace elements (Cu, Ni, Co and Mn) in bed and suspended sediments were used to evaluate the enrichment factor for anthropogenic influences and principal component analysis for identifying the origin of source contributions in the studied area. Normalization of metals to Fe indicated that high enrichment factors in the bed sediment were in the order of Co > Cu > Na > Ca > Ni except Mg, K and Mn while for suspended sediments, only Co has a high enrichment factor. High enrichment of Co and Cu reflected the contamination of sediments from anthropogenic sources. The high influence of Na and Ca in sediments may be caused for seawater salinization factor. A significant positive correlation among enrichment factors of various elements of interest suggests a common origin/identical behavior during transport in the sediment system. 相似文献
9.
以浙江沿海表层沉积物为研究对象,系统地研究了重金属有效结合态与沉积环境、矿物组成和人为排放等环境因素之间的相互关系.结果表明:沿海表层沉积物中重金属的积累数量,呈现出潮汐河口沉积物>沿海沉积物>强潮汐河口沉积物的趋势,这反映了不同沉积类型对重金属富集作用的差异;重金属的有效结合态,总体上以铁锰氧化物结合态>碳酸盐结合态>硫化物及有机结合态>可交换态的顺序存在,但是不同的重金属或同种重金属在不同的采点,主要有效结合态的比例存在明显的差异,这不仅与重金属的地球化学性质、沉积环境和沉积物中的粘土矿物组成有关,更受到重金属污染物的人为排放量的影响. 相似文献
10.
REE Mineralization of Weathered Crust and Clay Sediment on Granitic Rocks in the Sanyo Belt,SW Japan and the Southern Jiangxi Province,China 总被引：1，自引：0，他引：1
Rare earth element (REE) geochemistry and mineralogy have been studied in the weathered crusts derived from the Early Yanshanian (Jurassic) biotite granites of Dabu and Dingnan, as well as in the Indosinian (Permian) muscovite–biotite granite of Aigao in southern Jiangxi province, China, and the weathered crusts and clay sediments on biotite granites in the Sanyo belt, SW Japan, that is, Okayama, Tanakami, and Naegi areas. In all of the weathered crusts, biotite and plagioclase commonly tend to decrease toward the upper part of the profile, whereas kaolinite and residual quartz and K‐feldspar increase. The weathered crusts of the Dingnan granites and some Naegi granites, which are characterized by the enrichment in light REE (LREE) in C horizons, have higher total REE (ΣREE) content than the parent REE‐enriched granites. Weathering of LREE‐bearing apatite and fluorocarbonates in the Dingnan granites and allanite and apatite in some Naegi granites may account for the leaching of LREE at the B horizons. The leached LREE must result in subsequent enrichment of LREE in the C horizons. The enrichment is probably associated with mainly adsorption onto kaolinite and partly formation of possible secondary LREE‐bearing minerals. In Japan it was found that REE mineralization occurs not in the weathered granitic crusts but in reworked clay sediments, especially kaolinite‐rich layers, derived mainly from the weathering materials of REE‐enriched granitic rocks. The clay sediments are more enriched in LREE, which likely adsorbed onto kaolinite. Concentration of heavy REE within almost all the weathered crusts and clay sediments, however, may reflect mainly residual REE‐bearing minerals such as zircon, which originated in the parent granitic rocks. The findings of the present study support the three processes for fractionation of the REE during weathering: (i) selective leaching of rocks containing both stable and unstable REE‐bearing minerals; (ii) adsorption onto clay minerals; and (iii) presence of possible secondary LREE‐bearing minerals. 相似文献
11.
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). 相似文献
12.
Jian-bing Xu Bin Cheng Qian Deng Yun-gan Liang Oluwabamise Lekan Faboya Ze-wen Liao 《中国地球化学学报》2018,37(6):886-900
There is a dearth of information about the distribution of trace elements in kerogen from shale rocks despite several reports on trace element composition in many shale samples. In this study, trace elements in shale rocks and their residual kerogens were determined by inductively coupled plasma–mass spectrometry. The results from this study show redox-sensitive elements relatively concentrated in the kerogens as compared to the shales. This may be primarily due to the adsorption and complexation ability of kerogen, which enables enrichment in Ni, Co, Cu, and Zn. For the rare earth elements (REEs), distinct distribution characteristics were observed for shales dominated by terrigenous minerals and their kerogen counterparts. However, shales with less input of terrigenous minerals showed similar REE distribution patterns to their residual kerogen. It is speculated that the distribution patterns of the REEs in shales and kerogens may be source-related. 相似文献
13.
We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth. 相似文献
14.
Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment. 相似文献
15.
Jiafei Xiao Jingyang He Haiying Yang Chengquan Wu Jianbin Xu Yantao Li 《Resource Geology》2019,69(3):227-248
The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al2O3 and TiO2, SiO2, K2O, and Na2O, and strong negative correlations between Al2O3 and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K2O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ13C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO3? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter. 相似文献
16.
大同盆地是典型的干旱-半干旱内陆盆地,盆地中部地下水碘含量异常,对当地饮用水安全造成了严重威胁.对盆地高碘地下水分布区沉积物组成及稀土元素(REE) 进行了地球化学研究,结果表明,地下水系统呈弱碱性(pH值为7.18~9.64) 的偏还原环境,沉积物多为Ce正常或轻微负异常及Eu负异常;沉积物中碘含量为0~1.78×10-6;ΣREE含量较高,ΣLREE/ΣHREE比值为2.79~4.14,即富集轻稀土元素(LREE) 而亏损重稀土元素(HREE).ΣREE与碘含量呈负相关关系,虽然铁氧化物/氢氧化物矿物的还原性溶解可导致二者的释放,但由于沉积物有机质产生的低结晶矿物对碘的强吸附性,使沉积物中碘含量较高;弱碱性环境中REE的再吸附过程会导致沉积物中富集LREE;沉积物中碘含量与氧化还原敏感组分TOC、U、V及[Eu]N的关系也表明,地下水系统的氧化还原条件及有机质含量是影响碘富集的重要因素. 相似文献
17.
白云鄂博群黑色岩系微量元素地球化学特征及地质意义 总被引：3，自引：1，他引：3
白云鄂博群位于华北地台北缘,是一套中—新元古代裂谷沉积的产物。尖山组和比鲁特组是其中主要的黑色岩系。对以上两组中的碳质页岩和板岩的Au、Ag、As、Ba、Co、Cu、Hg、Mn、Mo、Ni、P、Pb、V、Zn、U、B、Sb等微量元素和稀土元素进行了较为详细的研究。通过元素含量特征、w(V)/w(V+Ni)、w(Zn)-w(Co)-w(Ni)三元图、稀土配分曲线、w(Ce)/w(La)、Ce和Eu异常、w(La)/w(Yb)-w(Ce)/w(La)和w(La)/w(Yb)-w(ΣREE)图解等方法对其沉积环境特征进行了探讨。微量元素含量分析显示白云鄂博群黑色岩系以富亲铜元素和亲石元素、贫亲铁元素为特征,其中富集Hg、B、As、Mn、Sb、Au、Ag、Pb、P、Ba、U、Mo等多种元素;较高的w(B)反映了黑色岩系沉积于盐度较高的水体中;高的w(V)/w(V+Ni)、w(Ce)/w(La)反映了黑色岩系形成于缺氧的沉积环境中;黑色岩系中Hg、Sb、Ba的富集和w(Zn)-w(Co)-w(Ni)图解中投点大部分靠近热水沉积区域指示了黑色岩系中有热水沉积物的参与;稀土元素配分模式、Ce和Eu异常及w(La)/w(Yb)-w(ΣREE)和w(La)/w(Yb)-w(Ce)/w(La)图解投点在两岩组中的不同特点表明尖山组沉积物以陆源沉积为主,有少量热水沉积物参与;而比鲁特组中热水沉积组分所占比例较大,形成时海水较深。 相似文献
18.
中国南方扬子地区下寒武统黑色页岩分布广泛,主要由黑色页岩、黑色白云质页岩,黑色粉砂质页岩和黑色硅质页岩等组成;并伴生有较厚的磷块岩矿床、钒矿床和镍、钼多元素硫化物矿床。对黑色页岩岩石学特征、元素地球化学特征进行系统研究,并详细分析微量元素的富集成因,结果表明：黑色页岩主要形成于静水还原的浅海-半深海缓坡环境,层状元素富集带为沉积成因,海底热流体提供了丰富物质来源。总体上,Co、Be、Mn、Ga等元素含量较低;Cu、V、Ni、Mo等元素的含量较高,多数超过北美页岩平均值;以Ni、Mo为主的多元素富集层通常位于磷块岩之上,以黑色页岩、黑色白云质页岩中的硫化物和硫酸盐矿物为主要载体,其中有机碳（TOC）含量可达12.2%以上,远高于其他元素富集层,随着页岩内硅质成分增加,Ni、Mo、Fe、Co等元素含量明显降低;以V为主的多元素主要赋存于黑色硅质页岩中的水云母,与页岩内硅质成分具有较好的正相关关系;黑色页岩中稀土元素含量为(76.22~290.67)×10-6,轻重稀土比值LREE/HREE介于1.21~4.22,说明轻稀土更为富集,Sr/Ba值为0.04~0.34,δEu正异常,且北美页岩标准化配分曲线呈现平缓左倾,为沉积过程中存在海底热水流体提供了进一步证据。 相似文献
19.
Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pKMHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pKMHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl−, F−, OH−, SO42−, CO32−, PO43−), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln3+) and sulfate complexes (LnSO4+) dominate, whereas in alkaline waters, carbonate complexes (LnCO3+ + Ln[CO3]2−) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter. 相似文献