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.     

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.     

Behaviour of rare earth elements at the freshwater–seawater interface of two acid mine rivers: the Tinto and Odiel (Andalucia, Spain)

The concentrations of dissolved and suspended particulate rare-earth elements (REE) are reported in acid-sulphate waters from the Odiel and Tinto rivers. Shale normalized patterns are typically convex and high REE concentrations (e.g., Ce=0.43–65 μg.l⁻¹) are present in the waters. The REE content of the suspended load is greater by a factor of up to 3000. In the Odiel river, REE patterns of the particulates are essentially convex and sub-parallel to those of the waters; speciation calculations indicate that SO₄ complexes play a dominant role in controlling the REE distributions. In the Tinto river, the REE patterns of the suspended load are slightly fractionated and a negative Ce anomaly is apparent in several samples, reflecting the local influence of phosphogypsum deposits.Contrasting with normal estuaries, REE are not intensely removed in the low chlorinity zone. A remobilization in relation to Fe reduction is observed in the Tinto river.     

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.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.     

Chemical and physical characterization of suspended particles and colloids in waters from the Osamu Utsumi mine and Morro do Ferro analogue study sites, Poços de Caldas, Brazil

Data are presented on suspended particles and colloids in groundwaters from the Osamu Utsumi mine and the Morro do Ferro analogue study sites. Cross-flow ultrafiltration with membranes of different pore sizes (450 nm to 1.5 nm) was used to prepare colloid concentrates and ultrafiltrates for analyses of major and trace elements and U- and Th-isotopic compositions. Additional characterization of colloidal and particulate material was performed by ESCA, SEM and X-ray diffraction. The results indicate the presence of low concentrations of colloids in these waters (typically < 500 μg/l), composed mainly of iron/organic species. Minor portions of uranium and other trace elements, but significant fractions of the total concentrations of Th and REE in prefiltered waters (< 450 nm) were associated with these colloids.Suspended particles (> 450 nm), also composed mainly of hydrous ferric oxides and humic-like compounds, show the same trend as the colloids with respect to U, Th and REE associations, but elemental concentrations were typically higher by a factor of 1,000 or more. In waters of low pH and with high sulphate content, these associations are considerably lower. Due to the low concentrations of suspended particles in groundwaters from the Osamu Utsumi uranium mine (typically <0.5 mg/l), these particles carry only a minor fraction of U and the REE (<10% of the total concentrations in unfiltered groundwaters), but a significant, usually predominant fraction of Th (30–70%). The suspended particle load in groundwaters from the Morro do Ferro environment is typically higher than in those from the mine by a factor of 5 to 10. This suggests that U, Th and the REE could be transported predominantly by particulate matter. However, these particles and colloids seem to have a low capacity for migration.     

Rare-earth elements in groundwaters from the Osamu Utsumi mine and Morro do Ferro analogue study sites, Poços de Caldas, Brazil

Data are presented on rare-earth elements (REE) in prefiltered (<450 nm) near-surface and deeper groundwaters and in corresponding particulate matter (>450 nm) from the Osamu Utsumi uranium mine and the Morro do Ferro thorium-REE-deposit. Groundwaters from both sites typically contain between 1–50 μg/l of total REE, but can reach values of up to 160 μg/l in the deepest borehole F4 (U-Mine: 150–415 m). Even higher REE concentrations of up to 29 mg/l were measured in acidic, sulfate-rich near-surface waters of the same site. The chondrite-normalized REE patterns in deeper, more reducing groundwaters and in their corresponding suspended particle fractions are similar to those observed in the bedrock (phonolites), indicating that bedrock leaching and secondary mineral sorption occurred without significant fractionation between these elements, in accordance with the only small variations in the stability constants of the expected REE-sulfate complexes in these waters. Groundwaters from the unsaturated zone of both sites show a very characteristic cerium depletion (less pronounced than that observed in the corresponding suspended particulate fractions), which is most probably related to the oxidation of Ce (III) under the prevailing E_h-conditions of these waters (600 to 800 mV), and to sorption/precipitation reactions of the much less soluble Ce(IV) species. Coarse particulate matter (>450 nm), composed mainly of amorphous ferric hydrous oxides, has a strong capacity for sorption of REE. This is shown by its very high REE concentrations, in some boreholes > 8,000 μg/g (total REE), and by the calculated association ratios R_a (ml/g), which are in the order of 10⁵ to 10⁶. The implications of these findings for the migration behavior of REE in both environments are discussed.     

Rare earth element transport and fractionation in small streams of a mixed basaltic–granitic catchment basin (Massif Central, France)

We present dissolved load (< 0.45 μm) rare earth element (REE) patterns of small streams from a catchment basin in the Massif Central in order to characterize the individual fractionation stages for the dissolved REE from the source to the catchment outlet. The upper part of the catchment is located on a basalt plateau, followed downstream by deep and narrow valleys with granitic and orthogneissic bedrock. Stream water has basalt-like REE patterns on the basaltic plateau close to the source, followed by a continuous depletion in light REE (La-Sm, LREE) downstream. Strontium and neodymium isotope ratios of stream water demonstrate that the dissolved REE are essentially of basaltic origin, even in the lower, granitic and gneissic part of the catchment. Mixing with gneiss or granite derived REE thus cannot explain the observed evolution of the REE patterns. There seems also to be no link with the calculated speciation of the dissolved REE. In contrast, a correlation between saturation indexes for hematite and La/Yb ratios suggests that REE fractionation is mainly controlled by precipitation of Fe-oxide particles that preferentially remove LREE from solution.     

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.     

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。     

Behavior of rare earth elements during mixing of different types of water (Kunashir,the Kurile Islands)

The fractionation of rare earth elements (REE) was evaluated under the conditions of natural acidic water mixing with fresh and sea waters using the example of unique objects on Kunashir Island (the Kislaya and Lesnaya rivers). It was shown that the concentrations and fractionation of REE in the water types considered are diverse and controlled by a number of factors. The concentrations of dissolved REE normalized to the North American Shale Composite show an increase from the light to the heavy REE, which reflects both the character of the REE input with the thermal waters and the more active sorption of the light REE and their preferential removal to suspended solids. This is supported by the similar REE patterns in the suspended matter of the Kislaya River. The mixing of the waters of the Kislaya and Lesnaya rivers, which are assigned to different chemical types, is accompanied by active REE coprecipitation with Fe, Al, and Mn oxides and the more extensive removal of the light REE compared with the heavy REE. During acidic water mixing with seawater, more than 80% of the REE were precipitated at a salinity of 8‰.     

The aqueous geochemistry of the rare earth elements and yttrium. Part 7. REE,Th and U contents in thermal springs associated with the Idaho batholith

Concentrations of the rare earth elements (REE), Th and U have been determined in thermal waters emerging from a number of locations in and around the Idaho Batholith. Previous investigators have suggested that the source of heat for the geothermal systems studied is the radioactive decay of K, Th and U which are enriched in the rocks through which the fluids flow. Thus, knowledge of the behavior of REE, Th and U in these systems may contribute to a better understanding of the potential consequences of the interaction of hydrothermal fluids with deeply buried nuclear waste. Such studies may also lead to the possible use of REE as an exploration tool for geothermal resources. The thermal waters investigated may be characterized as near-neutral to slightly alkaline, dilute, NaHCO₃-dominated waters with relatively low temperatures of last equilibration with their reservoir rocks (<200°C). REE, Th and U concentrations were measured using Fe(OH)₃ coprecipitation, followed by ICP-MS, which yielded detection limits of 0.01–0.003 μg/l for each element, depending on the volume of fluid sample taken. The concentrations of REE, Th and U measured (from <0.1 up to a few μg/l) are 3–5 orders of magnitude less than chondritic, in agreement with concentrations of these elements measured in other similar continental geothermal systems. The REE exhibit light REE-enriched patterns when normalized to chondrite, but when normalized to NASC or local granites, they exhibit flat or slightly heavy REE-enriched trends. These findings indicate that the REE are either taken up in proportion to their relative concentrations in the source rocks, or that the heavy REE are preferentially mobilized. Concentrations of REE and Th are often higher in unfiltered, compared to filtered samples, indicating an important contribution of suspended particulates, whereas U is apparently truly dissolved. In some of the hot springs the REE concentrations exhibit marked temporal variations, which are greater than the variations observed in major element concentrations, alkalinity and temperature. There are also variations in the fluid concentrations of REE, Th and U related to general location within the study area which may be reflective of variations in the concentrations of these elements in the reservoir rocks at depth. Thermal waters in the southern and central parts of the field area all contain ∑REE concentrations exceeding 0.1 μg/l (up to as high as 3 μg/l), Th exceeding 0.2 μg/l and U generally <0.4 μg/l. In contrast, thermal waters from the northern area contain lower ∑REE (<0.6 μg/l) and Th (<0.1 μg/l), but higher U (>3.0 μg/l). Using experimentally measured and theoretically estimated thermodynamic data, the distribution of species for La, Ce and Nd have been calculated and also the solubility of pure, endmember (La, Ce, Nd) phosphate phases of the monazite structure in selected hot spring fluids. These calculations indicate that, at the emergence temperatures, CO²⁻₃ and OH⁻ complexes of the REE are the predominant species in the thermal waters, whereas at the deep-aquifer temperatures, OH complexes predominate. In these thermal waters, monazite solubility is strongly prograde with respect to temperature, with solubility often decreasing several orders of magnitude upon cooling from the deep-aquifer to the emergence temperature. At the surface temperature, calculated monazite solubilities are, within the uncertainty of the thermodynamic data, comparable to the REE concentrations measured in the filtered samples, whereas at the deep-aquifer temperature, monazite solubilities are generally several orders of magnitude higher than the REE concentrations measured in the filtered or unfiltered samples. Therefore, a tentative model is suggested in which the thermal fluids become saturated with respect to a monazite-like phase (or perhaps an amorphous or hydrated phosphate) upon ascent and cooling, followed by subsequent precipitation of that phase. The temporal variations in REE content can then be explained as a result of sampling variable mixtures of particulate matter and fluid and/or variable degrees of attainment of equilibrium between fluid and solid phosphate.     

Trace elements in organic- and iron-rich surficial fluids of the boreal zone: Assessing colloidal forms via dialysis and ultrafiltration

On-site size fractionation of about 40 major and trace elements (TE) was performed on waters from boreal small rivers and their estuaries in the Karelia region of North-West Russia around the “Vetreny Belt” mountain range and in Paanajärvi National Park (Northern Karelia). Samples were filtered in the field using a progressively decreasing pore size (5 μm, 2.5 (3) μm, 0.22 (0.45) μm, 100 kDa, 10 and 1 kDa) by means of frontal filtration and ultrafiltration (UF) techniques and employing in-situ dialysis with 10 and 1 kDa membranes followed by ICP-MS analysis. For most samples, dialysis yields a systematically higher (factor of 2-3) proportion of colloidal forms compared to UF. Nevertheless, dialysis is able to provide a fast and artefact-free in-situ separation of colloidal and dissolved components.Similar to previous studies in European subarctic zones, poor correlation of iron concentration with that of organic carbon (OC) in (ultra)filtrates and dialysates reflect the presence of two pools of colloids composed of organic-rich and Fe-rich particles. All major anions and silica are present as dissolved species (or solutes) passing through the 1-kDa membrane. Size-separation ultrafiltration experiments show the existence of larger or smaller pools of colloidal particles different for each of the considered elements.The effect of rock lithology (acidic versus basic) on the colloidal speciation of TE is seen solely in the increase of Fe and some accompanying TE concentrations in catchment areas dominated by basic rocks compared to granitic catchments. Neither the ultrafiltration pattern nor the relative proportions of colloidal versus truly dissolved TE are affected by the lithology of the underlying rocks: within ±10% uncertainty, the two colloidal (10 kDa-0.22 μm and 1-10 kDa) and the truly dissolved (<1 kDa) pools show no difference in percentage of TE distribution between two types of bedrock lithology. The same conclusion is held for organic- and Fe-rich waters. In contrast, landscape context analysis demonstrated slight dominance, for most TE affected by UF, of large-size colloids (10 kDa-0.22 μm) in rivers and streams and small-size colloids and truly dissolved fractions in swamp stagnant surface waters. This supports the existence of two pathways of colloids formation: during the plant litter degradation in wetland zones and at the redox front in river riparian zone.     

Phospholipid ester-linked fatty acids composition of size-fractionated particles at the top ocean surface

Surface microlayer and subsurface water samples were collected at an oligotrophic Mediterranean site during a diel cycle. The composition of phospholipid ester-linked fatty acids (PLFA) was determined in size-fractionated particles (0.2–0.7 μm; 0.7–200 μm) in order to characterize the major contributors of organic matter to different size fractions. GF/F-retained particles (0.7–200 μm) from the surface microlayer were consistently enriched in PLFA relative to the underlying water. Molecular markers revealed a substantial difference in biological assemblages in both particle sizes. The larger particles were dominated by dinoflagellates, cyanobacteria, microzooplankton and attached bacteria, whereas particles filtered through GF/F and collected on 0.2 μm porosity Durapore filters (0.2–0.7 μm) were mostly bacteria and heterotrophic flagellates. Bacterial PLFA associated with 0.7–200 μm particles were more abundant than those in the 0.2–0.7 μm particles. Specific markers in the branched series appeared more representative of bacteria of smaller particle size.     

Rare earth elements in waters from the albitite-bearing granodiorites of Central Sardinia, Italy

With the aim of contributing to the knowledge of the geochemical behaviour and mobility of the rare earth element (REE) in the natural water systems, the ground and surface waters of the Ottana-Orani area (Central Sardinia, Italy) were sampled. The study area consists of albititic bodies included in Hercynian granodiorites. The waters have pH in the range of 6.0-8.6, total dissolved solid (TDS) of between 0.1 and 0.6 g/l, and major cation composition dominated by Ca and Na, whereas predominant anions are Cl and/or HCO₃.The pH and the major-element composition of the waters are the factors affecting the concentration of REE in solution. The concentrations of ∑REE+Y in the samples filtered at 0.4 μm vary between 140 and 1600 ng/l, with La of between 14 and 314 ng/l, and Yb of between <6 and 12 ng/l. A negative Ce anomaly, especially marked at high pH, is observed in the groundwaters. The surface waters show lower REE concentrations, which are independent of pH, and negligible Ce anomaly.Speciation calculations, carried out with the EQ3NR computer program, showed that the complexes with the CO₃²⁻ ligand are the dominant REE species at pH in the range of 6.7-8.6. The REE³⁺ ions dominate the speciation at pH <6.7 and only in the light REE (LREE).The relative concentrations of REE in water roughly reflect those in the aquifer host rocks. However, when concentrations of REE in water are normalised relative to the parent rocks, a preferential fractionation of heavy REE (HREE) into the water phase can be observed, suggesting the greater mobility and stability of HREE in aqueous solution.     

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.     

Geochemical behavior and speciation modeling of rare earth elements in acid drainages at Sarcheshmeh porphyry copper deposit,Kerman Province,Iran

Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln³⁺, Ln(SO₄)₂⁻, LnSO₄⁺, LnHCO₃²⁺, Ln(CO₃)₂⁻ and LnCO₃⁺. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO₄²⁻. High concentrations of SO₄²⁻ lead to the formation of stable LnSO₄⁺, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO₄⁺ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.     

Dissolved air flotation (DAF) of fine quartz particles using an amine as collector

Experimental studies concerning the dissolved air flotation (DAF) of fine (d_p < 100 μm) quartz particles, using two different flotation cells (setups), are presented. Pure and well characterised quartz samples were treated with a commercial amine as collector prior to flotation and bubbles were characterised by the LTM-BSizer technique. Bubble size distribution showed 71% (by volume) and 94% (by number) of the bubbles having sizes (d_b) lower than 100 μm (i.e. microbubbles). The Sauter and arithmetic mean diameters were 79 μm and 56 μm, respectively, for the bubbles generated at 300 kPa (gauge) saturation pressure (after 30 minute saturation time). Quartz particle size distribution (obtained by laser diffraction) showed a volume-moment diameter of 13 μm. The Rosin–Rammler–Bennett, Gates–Gaudin–Schumann and log-normal distribution functions were well fitted (R² > 0.96) to the bubble size distribution and quartz particle size distribution data. Values of total quartz recovery ranging from 6% to 53% (by mass) were obtained for the DAF experiments under different collector concentrations (up to 2 mg g^− 1), with an optimal collector concentration found at 1 mg g^− 1. These results are significant considering that 27% (by volume) of the quartz particles are ultrafine (d_p < 5 μm), demonstrating the widely-known efficiency of DAF to remove small particles when applied in the field of water and wastewater treatment. The true flotation behaviour, as a function of particle diameter (d_p), exhibits a local minimum when particles are approximately 3–5 μm in size. The results contribute to the discussion in the literature about the existence of such a minimum, which is generally interpreted as a change in the mechanism of particle collection from convection (collision) to diffusion at lower particle sizes.     

Major and trace element geochemistry in upper Ganga river in the Himalayas, India

Chemical weathering and resulting water compositions in the upper Ganga river in the Himalayas were studied. For the first time, temporal and spatial sampling for a 1 year period (monthly intervals) was carried out and analyzed for dissolved major elements, trace elements, Rare Earth Elements (REE), and strontium isotopic compositions. Amounts of physical and chemical loads show large seasonal variations and the overall physical load dominates over chemical load by a factor of more than three. The dominant physical weathering is also reflected in high quartz and illite/mica contents in suspended sediments. Large seasonal variations also occur in major elemental concentrations. The water type is categorized as HCO₃^––SO₄^2––Ca²⁺ dominant, which constitute >60% of the total water composition. On an average, only about 5–12% of HCO₃^– is derived from silicate lithology, indicating the predominance of carbonate lithology in water chemistry in the head waters of the Ganga river. More than 80% Na⁺ and K⁺ are derived from silicate lithology. The silicate lithology is responsible for the release of low Sr with extremely radiogenic Sr (⁸⁷Sr/⁸⁶ Sr>0.75) in Bhagirathi at Devprayag. However, there is evidence for other end-member lithologies for Sr other than carbonate and silicate lithology. Trace elements concentrations do not indicate any pollution, although presence of arsenic could be a cause for concern. High uranium mobilization from silicate rocks is also observed. The REE is much less compared to other major world rivers such as the Amazon, perhaps because in the present study, only samples filtered through <0.2 m were analysed. Negative Eu anomalies in suspended sediments is due to the excess carbonate rock weathering in the source area.