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。     

长江与黄河沉积物REE地球化学及示踪作用

长江与黄河沉积物的稀土元素（ＲＥＥ）组成特征不同。长江沉积物ＲＥＥ含量较高,元素含量变化也大于黄河样品;球粒陨石标准化模式表明长江沉积物的（Ｌａ／Ｌｕ）Ｎ、（Ｌａ／Ｙｂ）Ｎ、（Ｇｄ／Ｙｂ）Ｎ的值也相应地比黄河沉积物中的高１０％左右,分布曲线均呈明显的石倾状,轻重稀土分馏明显,相对富集ＬＲＥＥ。且长江样品比黄河样品更富集ＬＲＥＥ,但Ｅｕ亏损不及黄河样品;两者的北美页岩标准化曲线均呈平坦稍右倾状,具有     

Geochemical characteristics and provenance implication of rare earth elements in surface sediments from bays along Guangdong Coast, Southeast China

A systematic study of the granulometric properties and the occurrence and distribution of rare earth elements (REE) within surface sediments from ten bays situated along the coast of Southeast China has facilitated a more rigorous understanding of constraints on sediment provenance in the area. The results show that REE concentrations are similar within a single bay, but vary considerably (133.58–251.77 mg/kg) among the bays. The chondrite-normalized distribution patterns show the typical enrichment of light REEs (LREEs: La–Eu) relative to heavy REEs (HREEs: Gd–Lu), and an apparent depletion of Eu, which is diagnostic of a terrigenous sediment source. Obvious enrichments of the middle REEs (MREEs: Sm–Ho) in the PAAS-normalized (Post-Archean Australian Shale) distribution patterns of these bay sediments are similar to results reported from large rivers in China. Comparing the REE composition of the bay sediments with those of adjoining fluvial sediments and with the bedrock of the surrounding drainage basins, the latter are indicated as the dominant sediment source. The uniform REE distribution patterns, and MREE enrichments, prove that the sediments are derived from the material transported by the streams and rivers that discharge into the bays.     

Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

鄱阳湖流域赣江北支水体和沉积物中稀土元素的含量和分异特征

稀土的开发和广泛应用使得人们倍加关注其在环境中的分布及其环境地球化学行为。赣江作为鄱阳湖流域五大入湖河之一,发源于稀土资源富集的赣南地区,而其下游水体及周边地下水中稀土元素的含量和分异特征目前尚不完全清楚。以赣江北支水体及沉积物为研究对象,开展了稀土元素地球化学研究。结果表明,赣江北支水体中稀土元素总量在地表水中为230~1 146 ng/L(均值458.85 ng/L),地下水中为284~1 498 ng/L(均值634.94 ng/L),沉积物中稀土元素总量为177.9~270.7 mg/kg(均值226.99 mg/kg)。PHREEQC模拟计算表明,水体中的稀土元素主要以碳酸根络合物(REEC0₃⁺)的形式存在。地表水和地下水总体上均表现为重稀土元素相较于轻、中稀土元素富集,沉积物未表现出明显的富集特性;水体具有Ce、Eu负异常特点,而沉积物表现为Ce正异常和Eu负异常,指示氧化还原环境和水岩相互作用对稀土元素在水-沉积物系统中迁移转化的影响。地下水中稀土元素的含量沿流向具有上升趋势,而水体中重稀土元素的富集程度不断减弱,同时碳酸根络合物(REEC0₃⁺)的占比不断降低,反映水体中稀土元素的含量受到pH、胶体吸附、络合作用以及地下水-地表水相互作用的影响。水体中重稀土元素的富集受到碳酸根络合反应的影响,Ce、Eu负异常与Ce氧化沉淀和母岩特性相关。Gd异常值表明,研究区中下游水体中的Gd元素受到人为输入的影响。     

Rare Earth Element Patterns in the Karst Terrains of Guizhou Province, China: Implication for Water/Particle Interaction

The authors determine the concentrations of dissolved (<0.22 μm) rare earth elements (REE) and suspended particulate matter (SPM) of typical karst rivers in Guizhou Province, China during the high-flow period. The concentrations of acid-soluble REE extracted from SPM using diluted hydrochloric acid are also obtained to investigate water/particle interaction in the river water. The dissolved REE contents in the river water are extremely low in the rivers of the study. The dissolved REE distribution patterns normalized by the Post Archean Australia Shale (PAAS) in the karst rivers are not flat, show slight enrichment of heavy REE to light REE, and also have significant negative Ce and Eu anomalies. The acid-soluble REE appears to have similar distribution patterns as characterized by MREE enrichment and slight LREE depletion, with unremarkable Ce and Eu anomalies. The PAAS-normalized REE distribution patterns of SPM are flat with negative Eu anomalies. The contents and distribution patterns of REE in the SPM are closely related to the lithological character of the source rocks. The SPM contains almost all the REE produced in the process of surficial weathering. This demonstrates that particle-hosted REE are the most important form of REE occurrence. REE fractionation, which takes place during weathering and transport, leads to an obvious HREE enrichment in the dissolved loads relative to the SPM. Y/Ho ratio can be used to shed light on REE behaviors during water/particle interaction.     

Sources of stream sediments in the granulite terrain of the Walawe Ganga Basin,Sri Lanka,indicated by rare earth element geochemistry

Thirty-eight samples of stream sediments draining high-grade metamorphic rocks in the Walawe Ganga (river) Basin, Sri Lanka, were analysed for their REE contents, together with samples of metamorphic suites from the source region. The metamorphic rocks are enriched in light REE (LREE) compared to heavy REE (HREE) and are characterised by high La/Lu ratios and negative Eu anomalies. The chondrite-normalised patterns for these granulite-grade rocks are similar to that of the average post-Archaean upper crust, but they are slightly enriched with La and Ce. The REE contents of the <63-μm fraction of the stream sediments are similar to the probable source rocks, but the other grain size fractions show more enriched patterns. The <63-μm stream sediments fraction contains lower total REE, more pronouncd negative Eu anomalies, higher Eu_N/Sm_N and lower La _N/Lu_N ratios relative to other fractions. The lower La _N/Lu_N ratio is related to the depletion of heavy minerals in the <63-μm fraction. The 63–125-μm and 125–177-μm grain size fractions of sediments are particularly enriched in LREE (average ΣLREE=2990 μg/g and 3410 μg/g, respectively). The total HREE contents are surprisingly uniform in all size fractions. However, the REE contents in the Walawe Ganga sediments are not comparable with those of the granulite-grade rocks from the source region of the sediments. The enrichment of REE is accounted for by the presence of REE containing accessory mineral phases such as zircon, monazite, apatite and garnet. These minerals are derived from an unknown source, presumably from scattered bodies of granitic pegmatites.     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.     

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。     

Geochemical and mineralogical characteristics of recent clastic sediments from lower Godavari river: Implications of source rock weathering

The major, trace and rare earth elements geochemistry and clay mineral compositions in the river bed sediments from lower reaches of Godavari river suggest that they are derived from weathering of felsic rocks. Trace and rare earth elemental compositions indicate evidence of sedimentary sorting during transportation and deposition. Lower concentrations of transition elements, such as V, Ni and Cr imply enrichment of felsic minerals in these bed sediments. The REE pattern in lower Godavari sediments is influenced by the degree of source rock weathering. The light rare earth elements (LREE) content are indicating greater fractionation compared to the heavy rare earth elements (HREE). A striking relationship is observed between TiO₂ and gZREE content suggesting a strong control by LREE-enriched titaniferous minerals on REE chemistry. Shale-normalized REE pattern demonstrate a positive Eu anomaly, suggesting weathering of feldspar and their secondary products, which are enriched in Eu. Chondrite-normalised REE pattern is characteristic of felsic volcanic, granites and gnessic source rocks. Trace elemental compositions in sediments located near urban areas suggest influence of anthropogenic activity. Chemical Index of Alteration (CIA) is high (avg. 65.76), suggesting a moderate chemical weathering environment. X-ray diffraction analysis of clay fraction shows predominance of clay minerals that are formed because of the chemical weathering of felsic rocks.     

REE Mineralization of Weathered Crust and Clay Sediment on Granitic Rocks in the Sanyo Belt,SW Japan and the Southern Jiangxi Province,China

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.     

REE and their relevance to the development of the Kupferschiefer copper deposit in Poland

Over one hundred samples, representing mainly clayey-organic- and carbonate-rich shales (Kupferschiefer) but also other members of different ore sections, including hangingwall dolomites (Z1 Werra) and footwall Weissliegend sandstone (Lower Permian), have been collected in different mines of the Lubin–Głogów mining district, mainly near the contact (transitional zone) between the copper-mineralized zone and secondarily oxidized (Rote Fäule = RF) zone. In general, the Polish Kupferschiefer shales are enriched in MREE in comparison to NASC. In a typical copper-rich ore section the REE amounts and patterns depend on lithologies, being generally similar in shales and dolomite. ∑REE vary among sandstones, shales and dolomites (average 73, 143 and 85 ppm, respectively), probably reflecting mainly their clay contents. Sandstones have strongly convex REE patterns with positive Eu and negative Gd anomalies and depletion in LREE and enrichment in MREE relative to HREE. The REE patterns of shale and dolomite are similar to one another and rather flat, with strong negative Eu anomalies, and a small positive Gd anomaly in the case of shales.The REE patterns of shales from the mineralized Cu-zone are generally convex (MREE enriched) and have negative Eu anomalies. However, in a section with Cu-, Zn- and Pb-shales the REE pattern of Pb-bearing shales shows a positive Eu anomaly, in contrast to other shales and overlying dolomite. More oxidizing conditions of deposition can be assumed for Pb-shales.No significant differences between REE distributions in transitional and oxidized zones have been observed. Their REE patterns are more convex and are much higher (av. 247 ppm) than those in the mineralized zone and they do not show Eu anomalies. The strongly convex pattern may suggest either enrichment in MREE or relative depletion in LREE due to localized precipitation of light REE minerals, both in shales and in the uppermost part of the sandstones.Two unique sections, one Cu-rich and one Cu-lean (partly oxidized), comprising three shale beds interbedded with dolomites have been compared. Generally ∑REE contents are similar in these two sections. Also similar are changes in contents of REE between beds in both sections, which decrease significantly upwards (from 157–171 ppm to 54–60 ppm). The REE patterns of the lowermost beds (directly overlying sandstones) are ramp-like, with LREE enrichments. The upper beds have concave REE patterns. Comparison between sections shows generally stronger negative Eu and positive Gd anomalies in the highly-mineralized section.There is a highly significant positive relationship between Cu and ∑ REE contents in Cu-rich shales and slightly less significant negative relationship for their concentration in oxidized and transitional shales. There is a moderate significant positive correlation between P₂O₅ and ∑ REE contents in Cu-rich shales.The observed differences in REE contents cannot be provenance dependent but have been caused by diagenetic processes, possibly related to mineralization and oxidation processes. Europium anomalies, generally reflecting different Eh conditions in the deposit, can be eliminated by the prolonged oxidation. Strong enrichment of the RF zones in REE may result from their desorption from large volumes of oxidizing, including mineralizing, solutions which probably emerged from the underlying molasse lithologies into the Rote Fäule areas. Higher contents of REE in the lowermost shales suggest upward movement of solutions from the underlying sandstones also far away from the RF areas.     

Mineralogical control of rare earth elements in acid sulfate soils

Major, trace and rare earth element concentrations were measured in porewater, surface water and sediments at an acid sulfate soil site. The concentrations of La and Ce in porewater are up to 1-3 ppm. There is a strong correlation between REE concentration and acidity, except that the maximum concentrations were consistently found below the horizon of maximum acidity, associated with an increase in pH (to ca. 4) and change in mineralogy from jarosite-dominated to goethite-dominated mottles. Jarosite replacement by goethite is as expected with the rise in pH, which in turn is due to the occurrence of a fossil shell bed just below. The rare earth element patterns in the porewaters are enriched in the MREE with respect to Post-Archaean Australian Shale (PAAS). Measurements and calculations show that this is in accord with experiments on low-degree partial dissolution of jarosite, even when the jarosite itself is highly enriched in LREE. There is a clear fractionation in the patterns between the clay-rich soil matrix, which is slightly depleted in the LREE when normalized to PAAS (La/Yb_PAAS ∼0.5), and the secondary mineral phase jarosite, which is enriched in the LREE (La/Yb_PAAS = 15-50). The REE pattern in the porewater changes with the transition from jarosite- to goethite-rich mottles, becoming relatively more enriched in the LREE compared to the HREE, which is consistent with the incongruent dissolution of jarosite to form goethite and the release of greater amounts of jarosite REE to solution, including proportionately more of the jarosite-compatible LREE.Maximum surface water REE concentrations in acidic water were 100-200 ppb La and Ce. REE patterns in surface water were very similar to the porewater transition zone, enriched in the MREE, but asymmetric, relatively enriched in the LREE compared to the HREE.     

大同盆地沉积物REE分布特征及其对碘富集的指示

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.      

长江主要支流与干流沉积物的REE组成

系统采集了长江主要支流与干流从上游到下游不同地区的河漫滩沉积物样品,用1 M盐酸淋滤处理研究了REE在不同相态中的组成特征。研究表明,长江沉积物中REE主要赋存于酸不溶相中,约占总含量的70%。不同REE的酸提取效率不同,酸溶相明显富集REE,主要受磷灰石等磷酸盐矿物和部分Fe-Mn氧化物矿物的控制。主要赋存于粘土矿物中的不同轻稀土元素在酸溶相中百分比接近,而富重稀土元素的重矿物可以明显影响REE在不同相态中的组成和不同地区河流沉积物中REE的配分特征。长江支流沉积物的REE组成变化大于干流,流域源岩组成差异是控制REE组成的基本因素,但干流和支流沉积物全样与酸不溶相的REE配分模式基本类似,反映了各自流域风化上陆壳的平均组成。尽管一些支流对邻近干流沉积物的REE组成贡献较大,但总体上干流样品代表了不同支流水系沉积物的混合,尤其是下游近河口地区细粒级沉积物样品的酸不溶组分可以代表长江入海颗粒物的平均REE组成,用于示踪判别东部边缘海长江沉积物的源汇过程。     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

Rare-Earth Elements in the Atmospheric Precipitation of the City of Blagoveshchensk

The mineral composition, distribution and fractionation of rare-earth elements in dissolved and suspended forms (solid residue) of atmospheric precipitation were studied by analyzing the snow sampled over urbanized territory by the example of the city of Blagoveschensk. Electron-microscopic studies revealed the own minerals of rare-earth elements in dust aerosols. It is shown that the main sources of the atmospheric pollution by rare-earth elements were emissions of TPP (heat and power plants) and boiler houses. Contrasting geochemical anomalies of rare-earth elements were found in the snow cover of the city. The REE concentrations in the solid phase of snow are few orders of magnitude higher than those of the liquid phase. The snow solid phase provides insight into the REE behavior, because it directly reflects the impact of different anthropogenic sources. The characteristic feature of the REE distribution in the solid residue of snow is their LREE enrichment relative to MREE and HREE. The average HREE content is 10% of total REE. In the snow water–solid phase system, most samples show weak fractionation between LREE and HREE owing to the low total mineralization of the snow liquid phase and the small content of organic matter.     

Chemical and isotopic (B, Sr) composition of alluvial sediments as archive of a past hydrothermal outflow

The geochemical and isotopic signature of Quaternary alluvial sediments filling a post-orogenic basin along the Tyrrhenian coasts of Italy (Cornia Plain, Tuscany) was investigated to unravel possible interactions with geothermal fluids from the Larderello geothermal field. Two cores located in the upper (UCP) and lower (LCP) sector of the plain were sampled to depths of up to 80 m. A third core in a neighbouring area not affected by geothermal activity was also sampled (Arno plain at Pisa), and its sediment composition was used as reference. The Cornia sediments (fraction < 65 μm) show high B, Cs and Sb concentrations related to a peculiar chemical enrichment of the clay fraction. They also show remarkable enrichments in As (up to 1000 μg g^− 1) reflecting a contribution from local ore deposits.⁸⁷Sr/⁸⁶Sr ratios, ranging from 0.71022 to 0.71698, reveal the nature of the weathered mother rocks of the alluvial sediments, whereas the boron isotopic composition, varying from − 20‰ to − 10‰, suggests an interaction between the clay fraction and boron-rich fluids at temperatures greater than 50 °C. This implies that hydrothermal fluids widely circulated within the Cornia basin in the past, ultimately leading to the geochemical anomalies currently recorded in local sediments.Although natural (geogenic) in origin, these anomalies cause severe problems to the regional water management (groundwater exploitation) through leaching of trace elements into circulating groundwater, a phenomenon which has to be carefully studied and monitored.     

REE Geochemical Study of the Permian—Triassic Marine Sedimentary Environment in Guizhou Province

This paper deals with the REE geochemical characteristics of Permian-Triassic marine carbonate rocks in Guizhou Province.It is found that there are two broad categories of strati-graphic units in the region studied in accordance with their ΣREE contents and REE distribu-tion patterns: one is characterized by LREE enrichment and slight Ce depletion,with the REE distribution patterns similar to those of North American shales,and the other featrures relative HREE enrichment and relatively remarkable Ce depletion,with the REE distribution patterns close to those of pelagic sediments.In terms of their different ΣREE contents,five types of stratigraphic units can be distinguished.Incorporation of detrital minerals,REE complexing ca-pability,oxidation-reduction conditions of the media are the main factors affecting the REE com-position and REE distribution patterns of marine carbonate rocks in the region studied.In the light of REE geochemical characteristics of carbonate rocks,coupled with sedimentary facies analysis,this paper discusses the characteristics of the Permian-Triassic marine sedimentary environment in Guizhou Province and its evolutional rules.     

Geochemistry of rare earth elements in the modern sediments of Amur Bay (the Japan/East Sea)

The distribution of REE in the bottom sediments of Amur Bay accumulated over the last 100 years was studied, and the REE contents were evaluated. The REE contents normalized to North American Shale Composite (NASC) show a negative Ce anomaly and a predominance of LREE and MREE. The inflow and accumulation of REE in the bottom sediments are influenced mainly by natural sources, whereas their dependence on anthropogenic factors is minimal.