The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.     

鄱阳湖流域水化学特征及影响因素分析

在地球表生系统中,化学风化作用强烈改变着岩石、水体、土壤和大气成分,是元素地球化学循环的最主要驱动力。河水溶解物质主要来源于流域内岩石化学风化,同时受到降水、人类活动的影响。文中通过对鄱阳湖流域河水样品的采集和化学成分分析,结合流域地质背景,研究了河水化学成分特征及其影响因素。结果显示,与20世纪80年代相比,本区河水Cl-、SO24-所占比例显著增高,有逐渐酸化趋势;与世界上其他主要河流相比较,该区Ca2＋/Na＋、Mg2＋/Na＋、HCO3-/Na＋等比值偏低,反映了较强的蒸发岩溶解及人类活动影响特征。该区河水离子特征主要由岩石风化所控制,降水对该区河水溶解物质贡献率为10.3%,农业生产活动对鄱阳湖水溶解物质贡献率为4.9%,矿山活动对饶河丰水期、枯水期离子总量贡献率分别为8.9%、14.6%。     

Trace element chemistry of major rivers in Orissa State, India

 Geochemical analyses of surface waters from rivers flowing through Orissa State, India, indicated that trace element concentrations were extremely variable and consistently higher than world river average. The Brahmani River was the most solute-rich river studied, followed by the Baitarani and Mahanadi Rivers. Although all three rivers drain similar geology, the Brahmani River catchment is heavily industrialized, and water samples collected upstream and downstream from industries indicated that anthropogenic activity directly influenced its chemical composition. Samples collected from several towns, in all three river systems, did not invariably show similar patterns, with various elements having higher dissolved concentrations upstream. Because the concentration of total solids increased downstream, this implied that some components of the sewage had effectively sequestered available elements from solution and converted them to particulate material. Although the impact of pollution is clearly recognizable in water samples collected in proximity to the anthropogenic source, there are only slight elemental accumulations in the lower reaches of the Mahanadi River, with no accumulation in the Brahmani River. Apparently for these large rivers, discharged effluent becomes rapidly diluted, while complexation and sedimentation further removes trace elements from the water column. However, in the less voluminous Baitarani River, elementar enrichment near the river's mouth suggests that in this secondary river, where dilution effects are less, the concerns over regional water quality may be more prevalent. Received: 1 April 1995 · Accepted: 30 August 1995     

Seasonal and spatial variations in water chemistry and nitrate sources in six major Korean rivers

Seasonal and spatial variations in water chemistry and contaminant sources were investigated in six major rivers in South Korea that vary widely in drainage area and length. The dissolved-load content of the rivers varied seasonally, and some dissolved ions such as Cl^? and NO₃ ^? showed large spatial differences in all of the rivers. The water type changed from Ca–HCO₃ in the upper reaches to Na–Cl–NO₃ in the lower reaches, indicating anthropogenic contamination in the lower reaches. Compared with two relatively pristine rivers (the Sumjin and Mankyung rivers), the other four rivers, which flow through agricultural and urban areas, registered much higher Cl^? and NO₃ ^? concentrations. Statistical analysis showed that seasonal and spatial variations in water chemistry occurred in all the rivers. The nitrogen and oxygen isotopes of dissolved nitrate indicated that the rivers flowing through urban and agricultural areas were significantly affected by manure, sewage, or both.     

Distribution of trace elements in filtered and non filtered aqueous fractions: Insights from rivers and streams of Sardinia (Italy)

The distribution of several trace elements in different aqueous fractions has been studied in running waters from Sardinia (Italy). Trace elements and major components were determined in water samples collected at high- and low-discharge from rivers (90 samples) and streams (70 samples). At selected sites, total (non filtered samples) and dissolved (0.4 μm and 0.015 μm pore-size filtered samples) amounts of trace elements were determined, and the composition of the solid matter retained on the filters was investigated for estimating the eventual interrelationship. The elements B, Li, Rb, Sr, Ba, As, Sb, Mo, Tl and U in the studied waters showed small differences between total and dissolved amounts; dissolved concentrations were higher under low flow conditions, when the contribution of rainwater to the rivers was minimum; their concentrations were often correlated with total dissolved solids (TDS), and appeared to be related to the intensity of water-rock interaction processes. The elements Al, Fe, Mn, Pb, Zn, Cd, Cu, Co, Ni, Cs, Y, REE and Th were not related to TDS and/or major ions; they showed higher concentrations under high flow conditions; marked differences occurred between total and dissolved amounts; much lower concentrations were generally observed in the water filtered through 0.015 μm than in the water filtered through 0.4 μm, especially when sampling was carried out after heavy rain events that enhanced the load of solid matter in the water. These observations indicate an aqueous transport via sorption processes on very fine particles, such as Fe-oxide/hydroxide and clay mineral particles, which have been inferred by SEM-EDX analyses of the matter retained on the filters.     

湘西南区氧化锰矿成矿规律及找矿方向

湘西南区氧化锰矿以锰帽型氧化锰矿为主，赋矿地层为震旦系下统湘锰组。其特点是含锰点多，分布面广，矿体在地壳贫化，往下３～７ｍ开始富集，氧化深度４０ｍ左右。     

Geochemistry of tin in rivers and estuaries

On the basis of measurements from a large number of rivers from pristine and polluted regions, we estimate the riverine fluxes of tin to the oceans to be 0.76 × 10⁶molyr⁻¹ for the dissolved fraction and 300–600 × 10⁶ mol yr⁻¹ for the paniculate fraction. The paniculate flux agrees with the flux calculated from denudation rates. Estuaries were found not to have a large effect upon the transport of tin to the oceans. Evidence for the remobilization of tin was found in an estuary that is highly polluted with tin from mining and smelting activities. Monobutyltin was found to be present in polluted estuaries and is presumed to be a degradation product of tributyltin additives to antifouling paint.     

Himalayan uplift and osmium isotopes in oceans and rivers

Previous studies have shown that ¹⁸⁷Os/¹⁸⁸Os in seawater has become increasingly radiogenic over the last 40 Ma in a manner analogous to strontium. This rapid rise in the marine ¹⁸⁷Os/¹⁸⁸Os over the last 17 Ma has been attributed to an increase in the bulk silicate weathering rates resulting from the rise of the Himalayas and/or selective weathering and erosion of highly radiogenic organic rich ancient sediments. The key test of this hypothesis is the ¹⁸⁷Os/¹⁸⁸Os and the total osmium concentration of the Himalayan rivers. We report the concentration and isotopic composition of osmium in the Ganges, the Brahmaputra, and the Indus rivers. The ¹⁸⁷Os/¹⁸⁸Os of the Ganges close to its source (at Kaudiyal, 30°05′N, 78°50′E) is 2.65 and [Os] = 45 fM/kg. A second sample of the lower reaches of the Ganges at Patna (25°30′N, 85°10′E) gives ¹⁸⁷Os/¹⁸⁸Os =1.59 and [Os] = 171 fM/kg. The ¹⁸⁷Os/¹⁸⁸Os of the Brahmaputra at Guwahati (26°10′N, 91°58′E) is 1.07 and [Os] = 52 fM/kg. A sample of the Indus (Besham, 34°55′N, 72°51′E) has a ¹⁸⁷Os/¹⁸⁸Os of 1.2 and [Os] = 59 fM/kg. We infer that the Himalayas do not provide either a high flow of osmium or a highly radiogenic osmium component to the oceans. The overall trend for osmium and strontium could be explained by a regularly increasing input of global continental weathering sources but the Himalayas themselves appear not to be the dominant source.     

河流健康的定义与内涵

近年来,河流健康一词在学术论文、规划文件、媒体论坛、领导讲话中频繁出现,河流健康已成为当前学术界、领导者和公众共同关心的热门话题。这一现象表明,人们的可持续发展观念、人与自然和谐相处的认识和环境意识正在逐渐提高,是十分可喜的。然而,当我们对有关的论文、文件、领导讲话等关于河流健康的论述进行深入学习和分析时发现,人们对河流健康的理解还不深刻、不全面,甚至存在一些偏颇。什么是河流健康?它的内涵是什么?怎样描述河流的健康状况?怎样诊断一条河流是否健康?怎样保护、预警与修复河流的健康?对于这些问题,人们各抒己见,莫衷一是,显得较为混乱。显然,这是由于人们对河流健康概念的理解深度和差异造成的,这样的知识状况不利于我们正确指导和有效进行河流健康的评价与保护实践。基于上述,本刊邀请了部分专家、学者,举办本期笔谈,以期推动关于河流健康的研究和实践。     

河流中潜流交换研究进展

河水和地下水交换——潜流交换对溶质和污染物的归宿起着重要作用。潜流交换机理主要包括泵吸交换和冲淤交换。泵吸交换是由于河床形态引起的水头梯度,这些水头梯度诱导了对流传输;冲淤交换发生是由于移动河床截留和释放孔隙水。潜流交换的主要影响因素包括:河道流量、河床水力传导性、河床形态、河道弯曲、河床不均匀和背景条件。还探讨了反应性溶质、胶体颗粒共存情况下潜流交换的规律。对潜流交换研究现存的主要问题及未来研究展望提出了看法。     

自动电位滴定测定锰矿石中锰的方法研究

多批次的锰矿石锰含量滴定分析消耗大量人工,随着自动化电位滴定仪的普及,利用仪器完成容量滴定成为可能,而将手工滴定向自动电位滴定移植是当前需要解决的课题。本文建立了一套自动电位滴定仪测定锰矿石中锰含量的方法,确定了相关滴定参数和等当点识别标准。锰矿石样品采用盐酸、磷酸分解,硝酸去除碳和有机物,高氯酸氧化,形成样品溶液。自动电位滴定仪先用硫酸亚铁铵标准溶液对预先移取的重铬酸钾标准溶液和标定空白溶液分别进行氧化还原滴定,用铂复合电极指示,计算得到硫酸亚铁铵标准溶液浓度,再对样品空白溶液和样品溶液进行氧化还原滴定,得到样品锰含量,方法检测范围为5%～60%。采用本法分析国家一级标准物质,测定结果的准确度和精密度高;分析多个产地不同水平的锰矿石样品,测定结果与手工方法进行对照,经t检验无显著性差异。建立的滴定方法自动化程度高、方法稳健,适用于冶炼企业、港口商检等行业,具有推广价值。     

遵义铜锣井锰矿区土壤锰等元素的环境地球化学特征

对遵义铜锣井锰矿区及其背景区土壤的研究表明：（1）土壤母质岩石是控制土壤全量锰的主要因素，土壤有效锰受全量锰的制约。有效锰还受土壤物理化学条件的制约。总体上锰趋向于在表层土壤中富集。（2）土壤中锰的污染既有自然污染，也有人为污染。自然污染全量锰深层土壤大于浅层土壤；人为污染主要影响土壤表层，以表层土壤中高锰为特征，其深层土壤中锰与无污染状态相似。（3）锰矿开采造成的污染主要是锰的污染，其他元素如Cu，Zn，Co，Ni，Cd，Fe2O3，K2O污染不明显或无污染。土壤中全量P2O5可能受到了污染，但有效P2O5较低且分布无规律，反映不出锰矿开采造成的影响。     

河流分类体系研究综述

简要阐述河流分类的目的和方法,重点对基于地貌、水文、生态、价值的分类体系进行了回顾,按照时间顺序说明了各种分类体系的发展过程。河流分类体系不断走向系统与综合,体现在从单要素到多要素、从定性到定量、从结构到过程、从单尺度线状河流到多尺度等级系统,以及从自然系统到包含社会价值。随着河流生态学实验及理论的发展、多学科的合作以及多尺度数据源条件的改善,具有预测功能的分类体系将逐步取代描述性的分类体系。国际河流分类体系的研究成果对于我国多类型河流的生态恢复与管理具有重要的借鉴意义。     

Paleofloods and ancient fishing weirs in NW Iberian rivers

A 15-m-thick, fluvial sedimentary record of the NW Iberian lower Miño River was studied. Grain-size analyses were performed and twelve samples were dated using optically stimulated luminescence dating techniques, documenting a 1300-yr-old reconstructed fluvial record that does not match with known climate fluctuations in the area, but is linked instead to the construction of a series of ancient fishing weirs (pesqueiras). The sedimentation phases are in agreement with known episodes of increased population density, which suggests active use of the pesqueiras. A number of sedimentation hiatuses in the fluvial record point towards damage to the pesqueiras during large-scale flooding in the Miño River basin, and a sudden drop in population probably due to the arrival of the plague in the 13th century AD. The oldest sedimentation phases started just after 700 AD, and we infer that the first pesqueiras were constructed around this time. This timing coincides with the transition of the NW Iberian landscape towards a more intensively used agricultural landscape, as evidenced from other geo-archeological investigations. The results demonstrate that the pesqueiras are several hundreds of years older than known from historical records, but not so old as to date back to the Roman occupation.     

Manganese and Molybdenum in Phosphorites from the Ocean

The behavior of molybdenum and manganese is studied in phosphorite samples from shelves, seamounts, and islands of the ocean. In shelf phosphorites, molybdenum and manganese contents are 2–128 and 12–1915 ppm, respectively, while the Mo/Mn ratio ranges from 0.004 to 4.5. Phosphorites from oceanic seamounts impregnated with ferromanganese oxyhydroxides contain 0.84–14.5 ppm of Mo and 0.1–17% of Mn. The Mo/Mn ratio ranges within 0.0008–0.004. Phosphate-bearing ferromanganese crusts overlying the seamount phosphorites contain 54–798 ppm of Mo and 10–20% of Mn; Mo/Mn ratio varies within 0.002–0.005. Corresponding values for most island phosphorites are 0.44–11.2 ppm, 27–287 ppm, and 0.008–0.20, respectively. Phosphorites from reduced environments are characterized by a relative enrichment in Mo and depletion in Mn, whereas the Mo/Mn ratio reaches maximum values. The ratio decreases with transition to suboxic and oxic conditions. Molybdenum content in recent shelf sediments is commonly higher than that in authigenic phosphorites from these sediments. Recent phosphorite nodules from the Namibian shelf become depleted in Mo and Mn during their lithification, but Pliocene–Pleistocene nodules of similar composition and origin from the same region are enriched in Mo and characterized by a variable Mn content. The higher Mo content in phosphate-bearing ferromanganese crusts is a result of coprecipitation of Mo and Mn from seawater. Nonweathered phosphorites on continents and phosphorites from oceanic shelves are largely enriched in Mo with the Mo/Mn ratio ranging from 0.01 to 1.0. This is an evidence of their formation in reducing conditions.     

Computer simulation of sedimentation in meandering streams

A dynamic mathematical model for simulation of sedimentation in meandering streams is briefly described. This is composed of component mathematical models which are formulated to predict the following aspects of the system for a given physical situation and a single time increment. (1) The characteristics of the plan form of the meander; (2) the movement of the meander in plan, and definition of cross-sections across the meander in which erosion and deposition are considered in detail; (3) the hydraulic properties of the channel in the bend and the erosional and depositional activity within the channel as defined in specific cross-sections; (4) the nature and occurrence of cut-off; (5) a relative measure of the discharge during a seasonal high water period, which is used in (3) and (4); (6) aggradation. The model, in the form of a FORTRAN IV computer program, has been used to simulate various aspects of sedimentation in meandering streams by performing a set of experiments with the program under different input conditions. The geometry of simulated point bar sediments, as controlled by channel migration over floodplains with variable sediment type, agrees broadly with the natural situation, however extensive sheets of point bar sediment cannot be simulated because large scale meander-belt movements are not accounted for. In the simulated sediments, successive surfaces of the point bar before falling stage deposition (lateral and vertical) may be picked out, and these delineate the epsilon cross-stratification of Allen (1963b). The epsilon unit thickness is that measured from bankfull stage down to the lowest channel position existing prior to deposition. The model records the characteristic fining upwards of grain sizes in the point bar, and the systematic distribution of sedimentary structures. Channel migration combined with seasonal scouring and filling across the channel section produces a characteristic relief in the basal scoured surfaces and facies boundaries (as defined by variation in grain size and sedimentary structure). A related lensing and inter-fingering of the facies may also be present. The model also records large-scale lateral changes in grain size and sedimentary structure associated with changes in the shape of developing meanders. When channel migration is combined with a constant aggradation rate the model predicts a general slope (relative to the land surface) of facies boundaries and scoured basal surfaces upward in the direction of channel movement. If aggradation sufficiently increases the thickness of fine-grained overbank material, there is a channel stabilization effect. It is shown that a complete sequence of point bar sediments capped by overbank sediments would rarely be preserved in the moving-phase situation. Such preservation only becomes likely when an aggrading section lies out of range of an eroding channel for a considerably longer time span than it takes a meander to move one half-wavelength downvalley. Deep channel scours have a higher preservation potential than contemporary shallower ones. Where appropriate field data exist the model can be used in the more accurate recognition of ancient fluviatile sediments. Inferences may be made about the erosion-deposition processes operating in the ancient channel system, and the geometry and hydraulics of the system can be alluded to. A representative application of the model to the quantitative interpretation of an ancient point bar deposit is illustrated. There is reasonable agreement between the natural and the simulated deposits, and a broad quantitative picture of the palaeoenvironment of sedimentation is obtained.     

黔东地区锰矿选冶方法进展及对我国锰资源安全供给的意义

通过对黔东地区锰矿资源特点进行分析,简要介绍其选冶方法,并根据黔东地区锰矿储量情况,阐述了其对我国锰资源安全供给的意义。     

Manganese oxide mineralogy,petrography and genesis,Pilbara Manganese Group,Western Australia

Supergene manganese oxides, occurring in shales, breccias and dolomites of Proterozoic Age, in the Western Australian Pilbara Manganese Group, have Mn/Fe ranging from 1.9 to 254 and Mn⁴⁺ to Mn (Total) of 0.49–0.94. The manganese mineralogy is dominated by tetravalent manganese oxides, especially by cryptomelane, with lesser amounts of pyrolusite, nsutite, manjiroite, romanechite and other manganese oxide minerals. The manganese minerals are commonly associated with iron oxides, chiefly goethite, indicating incomplete separation of Mn from Fe during Tertiary Age arid climate weathering of older, manganiferous formations. These manganese oxides also contain variable amounts of braunite and very minor hausmannite and bixbyite. The braunite occurs in three generations: sedimentary-diagenetic, recrystallised sedimentary-diagenetic, and supergene. The mode of origin of the hausmannite and bixbyite is uncertain but it is possible that they resulted from diagenesis and/or low-grade regional metamorphism. The supergene manganese deposits appear to have been derived from manganiferous Lower Proterozoic banded iron formations and dolomites of the Hamersley Basin and overlying Middle Proterozoic Bangemali Basin braunite-containing sediments.     

Geochemistry of dissolved and particulate elements in the major rivers of China (The Huanghe,Changjiang, and Zhunjiang rivers)

The relationship between the geochemistry of dissolved and particulate materials and geographic conditions was investigated. Samples of water and suspended particulate matter were collected from five locations in three of the major rivers of China (the Huanghe, Changjiang, and Zhunjiang rivers). Because these rivers generally flow parallel to latitudes and flow through diverse geologic and climate zones, they provide excellent opportunities for comparisons of solute transport. The geochemistry of these rivers is influenced strongly by climate. The low discharge of the Huanghe River influences the character of the major ionic materials (Cl^?+SO₄ ^2? and Na⁺+K⁺) as well as the high degree of mineralization within the system. Dissolved concentrations of both major ions and trace elements are lower in the southern reaches of the rivers. The highly mobile ions, such as, Na⁺ and Ca²⁺, are depleted from the suspended particulate material in the southern regions, while the relatively immobile ions of Al, Fe, Ti, Mn, and trace metals are concentrated within the suspended mateiral. The relative mobility of some elements as measured by the Dissolved Transport Index (DTI) changes with climate. The geology of the area drained by the rivers has a major influence on the geochemistry in areas of similar climate. Lowest leaching rates in the southern climates occur in areas dominated by granite, which is resistant to weathering. The composition of both cations and anions among the three tributaries of the Zhujiang River are dependent on the rocks that dominate each eregion. Some particulate forms of the rare earth elements are present in the highest concentrations in regions dominated by granite. The DTI calculated for the major rivers in China are much smaller than those computed for other major rivers of the world. The low concentration of heavy metals in the particulate material suggests that pollution in the rivers of China is less serious than in rivers of other industrialized countries.