稀土元素分馏作用研究进展

本文综述了环境中稀土元素的分馏过程以及分馏作用对其在岩石、土壤、植物、水环境中分布、迁移规律的影响,探讨了引起稀土分馏的机理,为稀土的环境化学研究提供了详实的材料。     

High contents of rare earth elements (REEs) in stream waters of a Cu-Pb-Zn mining area

Stream waters draining an old mining area present very high rare earth element (REE) contents, reaching 928 microg/l as the maximum total value (sigmaREE). The middle rare earth elements (MREEs) are usually enriched with respect to both the light (LREEs) and heavy (HREEs) elements of this group, producing a characteristic "roof-shaped" pattern of the shale Post-Archean Australian Shales-normalized concentrations. At the Fenice Capanne Mine (FCM), the most important base metal mine of the study area, the REE source coincides with the mine tailings, mostly the oldest ones composed of iron-rich materials. The geochemical history of the REEs released into Noni stream from wastes in the FCM area is strictly determined by the pH, which controls the REE speciation and in-stream processes. The formation of Al-rich and mainly Fe-rich flocs effectively scavenges the REEs, which are readily and drastically removed from the solution when the pH approaches neutrality. Leaching experiments performed on flocs and waste materials demonstrate that Fe-oxides/oxyhydroxides play a key role in the release of lanthanide elements into stream waters. The origin of the "roof-shaped" REE distribution pattern as well as the peculiar geochemical behavior of some lanthanide elements in the aqueous system are discussed.     

Assessing the chemical behavior and spatial distribution of yttrium and rare earth elements (YREEs) in a coastal aquifer adjacent to the Urmia Hypersaline Lake,NW Iran

This study aims to shed light on the seasonal behavior of yttrium and rare earth elements (YREEs) in the Urmia Aquifer (UA), in the immediate vicinity of Urmia Lake (UL) in Iran. Samples of groundwater, collected under dry and wet conditions in coastal wells of UA, suggest a large degree of variability in both YREE abundance and normalized patterns. Although weathering or water-rock interactions (between the surface/groundwater and rock samples) were predicted to be the most probable source in explaining YREEs in groundwater samples, results to the contrary indicate that the groundwater do not inherit aquifer rock-like YREE signatures in the study area; this might be due to the relative stability of YREEs during the process of water-rock interactions, which suggest that methods based on YREEs can be beneficial in discrimination of water sources. Furthermore, findings demonstrated no significant relationship between Ce/Ce* and salinity (0.08 and 0.05 in wet and dry seasons, respectively), and between Eu/Eu* and salinity (0.1 and ?0.04 in wet and dry seasons, respectively). Dissimilarity of patterns of YREEs in rock and water samples reveals YREEs as no conservative tracers in determining the UL saltwater intrusion into coastal groundwater. Therefore, the groundwater YREE concentrations and fractionation patterns in UA warrant controlling by coastal aquifer need to be controlled by other chemical weathering, adsorption, desorption, and solution complexation reactions. Finally, comparison of REE concentration values in groundwater samples with corresponding indicative admissible drinking water concentrations (IAC) demonstrated their suitability for drinking purposes.

     

The fractionation and geochemical characteristics of rare earth elements measured in ambient size-resolved PM in an integrated iron and steelmaking industry zone

Environmental Science and Pollution Research - Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due...     

Natural pollution caused by the extremely acidic crater lake Kawah Ijen, East Java, Indonesia

Background. Aims and Scope Lakes developing in volcano craters can become highly acidic through the influx of volcanic gases, yielding one of the chemically most extreme natural environments on earth. The Kawah Ijen crater lake in East Java (Indonesia) has a pH 〈 0.3. It is the source of the extremely acid and metal-polluted river Banyupahit (45 km). The lake has a significant impact on the river ecosystem as well as on a densely populated area downstream, where agricultural fields are irrigated with water with a pH between 2.5 and 3.5. The chemistry of the river water seemed to have changed over the past decade and the negative effect in the irrigation area increased. A multidisciplinary approach was used to investigate the altered situation and to get insight in the water chemistry and the hydrological processes influencing these alterations. Moreover, a first investigation of the effects of the low pH on ecosystem health and human health was performed. Methods Water samples were taken at different sites along the river and in the irrigation area. Sampling for macroinvertebrates was performed at the same sites. Samples of soil and crop were taken in the irrigation area. All samples were analysed for metals (using ICP-AES) and other elements, and concentrations were compared to local and international standards. Results and Discussion The river carries a very high load of SO4, NH4, PO4, Cl, F, Fe, Cu, Pb, Zn, Al and other potentially toxic elements. Precipitation and discharge data over the period of 1980 – 2000 clearly show that the precipitation on the Ijen plateau influences water chemistry of the downstream river. Metal concentrations in the river water exceed the concentrations mentioned in Indonesian and international quality guidelines, even in the downstream river and the irrigation area. Some metal concentrations are extremely high, especially iron (up to 1600 mg/l) and aluminium (up to 3000 mg/l). The food-webs in the acidic parts of the river are highly underdeveloped. No invertebrates were present in the extremely acid water and, at pH 2.3, only chironomids were found. This also holds true for the river water with pH 3.3 in the downstream area. Agricultural soils in the irrigation area have a pH of 3.9 compared to a pH of 7.0 for soils irrigated with neutral water. Decreased yields of cultivated crops are probably caused by the use of Al containing acid irrigation water. Increased levels of metals (especially Cd, Co, Ni and Mn) are found in different foodstuffs, but still remain within acceptable ranges. Considering local residents” diets, Cd levels may lead to an increased risk for the human health. Fluoride exposure is of highest concern, with levels in drinking water exceeding guideline values and a lot of local residents suffering from dental fluorosis. Conclusions, Recommendations and Outlook In short, our data indicate that the Ijen crater lake presents a serious threat to the environment as well as human health and agricultural production.     

Distribution of selected heavy metals and rare earth elements in surficial sediments from the polish sector of the Vistula Lagoon

The concentrations of 22 trace elements plus the rare earth elements (REE) were determined in the <63 μm fraction of surficial sediments from the Polish sector of the Vistula Lagoon by ICP-MS. For the anthropogenically-enriched elements, the mean element enrichment factors (EF's) decrease in the sequence Ag (9.9) > Sb (7.5) >As (5.8) ≥ Cd (5.2) > Pb (3.7), albeit with large variability in concentration in the sediments from one station to another. These observations demonstrate that sediments from the Vistula Lagoon are locally polluted by these anthropogenically-derived elements. Plots of NASC-normalized REE data show that the REE patterns of the sediments have not been significantly modified during transport from their source with only a minor depletion of the heavy rare earth elements (HUE) compare to the light rare earth elements (LREE). The lack of any significant anomalies for Ce and Eu indicates that redox processes have not played a major role in modifying the distribution of the REE. Factor ananalysis of the compositional data shows that sediments from the Polish sector of the Vistula Lagoon can be divided into three main groups depending on the geographical location and the degree of contamination by heavy metals.     

Rare earth elements in naturally grown fern Dicranopteris linearis in relation to their variation in soils in south-Jiangxi region (southern China)

Ferns (Dicranopteris linearis) and soils, sampled from four rare earth mining areas and one non-mining area locating in South-Jiangxi region, were chosen for analysis of 15 rare earth elements (REEs) by inductively coupled plasma-mass spectrometry (ICP-MS). The fern samples were divided into 4 parts: root, stem, petiole, and lamina. The soils of the same sites were also sampled, and 4 soil layers were observed at the profile: A (0-20 cm depth), B (20-150 cm depth), C (150-400 cm depth), and D (rock). The distribution patterns and transportation characteristics of REEs of different soil layers and of different parts of D. linearis were studied. The results showed that in the soil layers, the sigma REE (the sum of the concentrations of 15 REEs) of A layer, as well as B layer were lower than that of C layer, but Ce was relatively concentrated in A layer. The sigma REE of different parts of D. linearis were lamina, root > stem > petiole. The REE distribution patterns of D. linearis root were similar to the total REE distribution patterns of the A layer of their host soils, especially to the soluble REE distribution patterns of the A layer of their host soils. The REEs were fractionated in their transportation in D. linearis. The abundances of heavy rare earth elements (HREEs, Gd to Lu and Y) in the stem, petiole, lamina are lower than those in the root.     

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin,Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary–Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.     

The effect of hydrological factors on trace metal contamination in the river Tawe, South Wales

The concentrations of nickel, copper, iron, chromium, lead, cadmium, manganese and zinc have been studied in a small river in South Wales. The river drains the contaminated industrial wasteland of the Lower Swansea Valley which is currently undergoing redevelopment and landscaping activity. The high trace metal levels found in the river waters result from weathering and erosion of this waste material, as well as from two industrial point sources of nickel, and iron and chromium. Hydrological factors found to be of importance in determining current spatial and temporal patterns of contamination included: (1) the river's available dilution at any one time, (2) antecedent river flow conditions, (3) river water pH and (4) the prevailing runoff processes in operation at any one time. The metals are present mostly in their dissolved state (i.e. > 70%), with the exception of iron and chromium which are present mostly as particulates (i.e > 80%).     

Fractionation and composition of colloidal and suspended particulate materials in rivers

The association of pollutants (nutrients, heavy metals and organic compounds) with colloidal and suspended particle matter (SPM) plays a dominant role in determining their transport, fate, biogeochemistry, bioavailability and toxicity in natural waters. A scheme for the fractionation and composition of colloidal and SPM from river waters has been tested. All four separation methods, i.e. sieving, continuous flow centrifugation, tangential flow filtration, sedimentation field-flow fractionation, were for the first time used to separate five size particulate fractions from river. Significant (gram) amounts of colloidal material (<1 microm) in three size ranges, nominally 1-0.2, 0.2-0.006 and 0.006-0.003 microm were obtained. The separation scheme was able to process large samples (100 l), within reasonable times (1 day) and the apparatus was portable. The aquatic colloid size was also characterized with high resolution by using sedimentation field-flow fractionation technique. The mass-based particle size distribution for the water sample showed a broad size distribution between 0.05 and 0.4 microm with the maximum around 0.14 microm. There was a systematic increase in the content of organic carbon (estimated by loss on ignition), Mg, Ca, Na, Cu and Zn with decreasing particle size, highlighting the importance of the colloidal (<1 microm) fraction. It was concluded that the colloidal Cu and Zn concentrations in rivers might be much higher than those reported before.     

Effect of earthworms (Eisenia fetida) on the fractionation and bioavailability of rare earth elements in nine Chinese soils

The effect of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), fraction distribution pattern and bioavailability of rare earth elements (REEs) Y, La, Ce, Pr and Nd in nine Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community (Standards, Measurements and Testing Programme) was used to fractionate REEs in soils into water soluble, exchangeable and carbonate bound (B1), Fe- and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). Inoculated with earthworms, the soil pH, DOC and water-soluble rare earth elements fraction increased. A significant correlation was obtained between the increased DOC and the increased water-soluble REEs. REEs in fraction B1 increased after earthworm inoculation, while those in fraction B3 decreased. No significant differences were observed for REEs in fraction B2. The biomass and the concentrations of REEs in wheat shoots and roots increased after the treatment with earthworms. The results demonstrated that earthworm activity increased the mobility and bioavailability of REEs in soils.     

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation–proton exchange with HA (i.e., pK_MHA) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK_MHA values is more suitable for use in Model V for the simulation of REE complexation with HA.     

Antioxidant response of soybean seedlings to joint stress of lanthanum and acid rain

Excess of rare earth elements in soil can be a serious environmental stress on plants, in particular when acid rain coexists. To understand how such a stress affects plants, we studied antioxidant response of soybean leaves and roots exposed to lanthanum (0.06, 0.18, and 0.85 mmol L^?1) under acid rain conditions (pH 4.5 and 3.0). We found that low concentration of La³⁺ (0.06 mmol L^?1) did not affect the activity of antioxidant enzymes (catalase and peroxidase) whereas high concentration of La³⁺ (≥0.18 mmol L^?1) did. Compared to treatment with acid rain (pH 4.5 and pH 3.0) or La³⁺ alone, joint stress of La³⁺ and acid rain affected more severely the activity of catalase and peroxidase, and induced more H₂O₂ accumulation and lipid peroxidation. When treated with high level of La³⁺ (0.85 mmol L^?1) alone or with acid rain (pH 4.5 and 3.0), roots were more affected than leaves regarding the inhibition of antioxidant enzymes, physiological function, and growth. The severity of oxidative damage and inhibition of growth caused by the joint stress associated positively with La³⁺ concentration and soil acidity. These results will help us understand plant response to joint stress, recognize the adverse environmental impact of rare earth elements in acidic soil, and develop measures to eliminate damage caused by such joint stress.     

Scandium,yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Go? soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

     

Aerobic dehalogenation potentials of four bacterial species isolated from soil and sewage sludge

In Polar regions subject to acid precipitation, the spring flood period is swift and can be divided into three phases. In phase one, dilution and anion substitution by SO4 controls episodic acidification. Phase two is characterized by interaction of snowmelt water with the catchment. A combination of several factors contributes to declines in pH and ANC. In forest and wetland ecosystems, organic acids greatly contribute to the pH depression in the streams. In the coastal tundra and forest-tundra zones, "salt-effect" acidification predominantes. The increase in toxic forms of trace (Ni, Cu) and rare (Fe, Al, Mn) elements during pH depressions may create stress conditions for the fauna of polar fresh waters during a flood period.     

Trace element uptake by Eleocharis equisetina (spike rush) in an abandoned acid mine tailings pond, northeastern Australia: implications for land and water reclamation in tropical regions

This study was conducted to determine the uptake of trace elements by the emergent wetland plant species Eleocharis equisetina at the historic Jumna tin processing plant, tropical Australia. The perennial emergent sedge was found growing in acid waters (pH 2.45) and metal-rich tailings (SnAsCuPbZn). E. equisetina displayed a pronounced acid tolerance and tendency to exclude environmentally significant elements (Al, As, Cd, Ce, Co, Cu, Fe, La, Ni, Pb, Se, Th, U, Y, Zn) from its above-substrate biomass. This study demonstrates that geobotanical and biogeochemical examinations of wetland plants at abandoned mined lands of tropical areas can reveal pioneering, metal-excluding macrophytes. Such aquatic macrophytes are of potential use in the remediation of acid mine waters and sulfidic tailings and the reclamation of disturbed acid sulfate soils in subtropical and tropical regions.     

Historical and current atmospheric deposition to the epilithic lichen Xanthoparmelia in Maricopa County,Arizona

Spatial patterns of atmospheric deposition of trace elements to an epilithic lichen were assessed using a spatial grid of 28 field sites in 1998 throughout Maricopa County, Arizona, USA. In addition, samples of Xanthoparmelia spp. from Arizona State University lichen herbarium material (1975-1976) was utilized for a limited number of sites in order to explore temporal trends. The lichen material was cleaned, wet digested and analyzed by ICP-MS for a suite of elemental concentrations [antimony (Sb), cadmium (Cd), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), dysprosium (Dy), europium (Eu), gadolinium (Gd), gold (Au), holmium (Ho), lead (Pb), lutetium (Lu), neodymium (Nd), nickel (Ni), palladium (Pd), platinum (Pt), praseodymium (Pr), samarium (Sm), scandium (Sc), silver (Ag), terbium (Tb), thulium (Tm), tin (Sn), uranium (U), ytterbium (Yb), yttrium (Y), and zinc (Zn)]. Cluster analysis and principal component analysis suggest three major factors, which, depending on regional aerosol fractionation, explain most of the variation in elemental signatures: (1) a group of widely distributed rare earth elements (2) a highly homogenous Co, Cr, Ni, and Sc component representing the influence of mafic rocks, and (3) anthropogenic emissions. Elemental concentrations in Maricopa County lichens were generally comparable to those reported for relatively unpolluted areas. Only highly urbanized regions, such as the greater Phoenix Metropolitan Area and the NW corner of the county, exhibited elevated concentrations for Zn, Cu, Pb, and Cd. Lead levels in lichens have fallen over the last 30 years by 71%, while Zn concentrations for some regions have increased by as much as 245%. From the spatial pattern of elemental deposition for Cd, Cu, Ni, Pr, Pb, and Cu, we infer that agriculture, mining, industrial activities, and traffic probably are the major air pollutant sources in Maricopa County.     

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.     

Chemical speciation and bioavailability of rare earth elements (REEs) in the ecosystem: a review

Rare earths (RE), chemically uniform group of elements due to similar physicochemical behavior, are termed as lanthanides. Natural occurrence depends on the geological circumstances and has been of long interest for geologist as tools for further scientific research into the region of ores, rocks, and oceanic water. The review paper mainly focuses to provide scientific literature about rare earth elements (REEs) with potential environmental and health effects in understanding the research. This is the initial review of RE speciation and bioavailability with current initiative toward development needs and research perceptive. In this paper, we have also discussed mineralogy, extraction, geochemistry, analytical methods of rare earth elements. In this study, REEs with their transformation and vertical distribution in different environments such as fresh and seawater, sediments, soil, weathering, transport, and solubility have been reported with most recent literature along key methods of findings. Speciation and bioavailability have been discussed in detail with special emphasis on soil, plant, and aquatic ecosystems and their impacts on the environment. This review shows that REE gained more importance in last few years due to their detrimental effects on living organisms, so their speciation, bioavailability, and composition are much more important to evaluate their health risks and are discussed thoroughly as well.     

Heavy metals in coastal water systems. A case study from the northwestern Gulf of Thailand

A geochemical survey of the northwestern part of the Thailand Gulf (Inner Gulf) was carried out in order to define concentrations and distribution patterns of selected heavy metals (V, Cr, Co, Ni, Cu, Zn, and U) in the coastal system and estuarine area of the Mae Klong river. The results indicate the presence of two different sources of heavy metals in the studied environment and allowed us to identify a lithogenic component that significantly influences the composition of coastal waters and suspended particulate matter (SPM). Comparison of the normalized heavy metals concentrations both in the studied samples and in those reported for the Sn-W ores present in the surrounding areas suggests an important anthropogenic contribution to the chemistry of the seafloor sediments. Vanadium and nickel enrichment factors (EF) calculated for coastal waters indicate that contamination by hydrocarbons discharge took place in the investigated area.