Levels of rare earth elements on three abandoned mining sites of bauxite in southern Italy: A comparison between TXRF and ICP-MS.

The essential utilization of rare earth elements (REEs) for the production of several electronic devices is making the demand for them being increased all the time. This extensive use of these elements has also increased concern about human and environmental health. Previous studies have shown that REE levels are higher in environmental samples near mining sites, and they are highly possible to be transferred to biota. In this study, REE levels were determined in environmental samples collected from three abandoned mining sites of bauxite (Gargano, Otranto, and Spinazzola) in the region of Puglia, Southern Italy. The samples were digested and analyzed by two different techniques, Total X-Ray Fluorescence (TXRF) and Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS) to investigate which technique is the most suitable for analysis of the REE content in samples from abandoned mining sites of bauxite. Only 6 REEs could be detected by TXRF, while all REEs were detected in all the samples by ICP-MS. Spinazzola is the richest site and Ce the most abundant REE in all three regions. REE levels are correlated between the soil and biota samples in many cases, although the calculation of the bioconcentration factor showed that REEs are not bioaccumulative. ICP-MS seems to be a more suitable technique for analysis of the whole REE content in environmental samples from abandoned mining sites of bauxite.

Decoupling of scandium and rare earth elements in organic (nano)particle-rich boreal rivers draining the Fennoscandian Shield.

Only few datasets on scandium (Sc) and rare earths and yttrium (REY) in rivers are available and the behaviour of Sc in the hydrosphere is poorly understood. We determined Sc and REY concentrations in the dissolved fraction of twelve boreal rivers in Sweden, which show low conductivity, circumneutral pH and elevated dissolved organic carbon (DOC). Scandium concentrations vary between 189 and 1170 pmol/l and are at the high end of the range reported for rivers worldwide. Unusually high Sc concentrations in the Dalsälven and Västerdalälven could be tracked to the Vanån, a tributary to the headwaters of the latter. Increasing Sc with increasing DOC and Yb concentrations suggest that organic ligands play a major role in the distribution of Sc. The REYSN patterns are similar for all rivers (except the Västerdalälven) and are slightly light REY-depleted with negative Ce and Eu anomalies, and positive Y anomalies. These patterns appear to be a general feature of freshwater draining the Fennoscandian Shield into the Baltic Sea for at least the past 28 years. Our results clearly demonstrate that Sc and REY are fractionated in river waters relative to their crustal source and that they should not be discussed jointly as "REE".

Naturally grown duckweeds as quasi-hyperaccumulators of rare earth elements and yttrium in aquatic systems and the biounavailability of gadolinium-based MRI contrast agents.

The use of rare earths and yttrium (REY) in high-technology products is accompanied by their increasing release into the environment. Concerns regarding the (eco-)toxicity and bioaccumulation of these emerging contaminants highlight the need for research on REY uptake by (aquatic) plants. Duckweeds are widespread macrophytes in lentic waters and receive increasing attention as a potential protein-rich food additive. We here provide a baseline dataset for the complete set of REY in naturally grown duckweed assemblages and ambient freshwater and coastal brackish seawater. Our results show that duckweeds strongly bioaccumulate REY and incorporate them at the µg/kg level (dry matter basis). Their shale-normalised (SN) REY patterns are mildly fractionated relative to upper continental crust, regardless of sampling location and season. In contrast, the patterns of ambient waters increase from light to heavy REY (LREY and HREY, resp.) and may show prominent positive anthropogenic GdSN anomalies due to the presence of Gd-based contrast agents (Gd-CAs) applied for magnetic resonance imaging (MRI). The lack of GdSN anomalies in the duckweed assemblages reveals discrimination against the uptake of Gd-CAs by the macrophytes, providing further evidence for the conservative behaviour of these xenobiotics in the environment. High REY concentrations and apparent bulk distribution coefficients between duckweeds and ambient waters of up to 105 show that duckweeds are quasi-hyperaccumulators of REY. Uptake of LREY is up to two orders of magnitude higher than of HREY, possibly due to stronger complexation of HREY with dissolved ligands. The REY closely correlate with Mn but not with Ca, suggesting that uptake of REY and Mn occurs via the same pathway and revealing the negligible role of calcium oxalates. Our study demonstrates that while duckweeds are quasi-hyperaccumulators of REY, there is currently no risk that anthropogenic Gd from MRI contrast agents may enter the food chain via consumption of duckweeds.

Highly Siderophile Elements and Coupled Fe-Os Isotope Signatures in the Temagami Iron Formation, Canada: Possible Signatures of Neoarchean Seawater Chemistry and Earth's Oxygenation History.

Banded iron formations (BIFs) were deposited before and concurrent with the Great Oxidation Event at ∼2.33 Ga. They provide useful archives that document the transformation of the Precambrian hydrosphere from anoxic to progressively oxygenated conditions. Their formation involves removal of oceanic Fe by either inorganic or biologically promoted Fe2+ oxidation, or both. To evaluate depositional settings, elemental sources that affect seawater chemistry, and oxidation pathways, we present the first combined highly siderophile element (HSE) and Fe-Os isotope study for the ∼2.7 Ga Temagami BIF, Abitibi Greenstone Belt, Ontario (Canada). HSE abundances and 187Os/188Os ratios show no systematic variation between alternating magnetite and (meta)chert bands of the Temagami BIF. Whereas HSE concentrations mostly resemble modern crustal values, present-day 187Os/188Os ratios range from ∼0.17 to ∼10.8. Magnetite samples define a regression line corresponding to an age of 2661 ± 126 Ma. A chondrite-like 187Os/188Os initial value is in agreement with earlier studies on Neoarchean marine sediments and is thought to reflect seawater composition, which, unlike modern oceans, is dominated by mantle-like 187Os inventory most likely derived from deep-sea hydrothermal vents. Our δ56Fe data vary from about +0.6‰ to +0.9‰ and define a sawtooth-like pattern between alternating magnetite and (meta)chert layers. Partial oxidation of hydrothermally sourced Fe(II) and a lack of microbially mediated dissimilatory iron reduction provide the most plausible explanation for the positive δ56Fe values. Notably, our δ56Fe data for Temagami are in accord with trends defined by literature results for other Algoma-type BIFs that were deposited throughout the Archean.

Potential of garnet sand as an unconventional resource of the critical high-technology metals scandium and rare earth elements.

Scandium is a critical raw material that is essential for the EU economy because of its potential application in enabling technologies such as fuel cells and lightweight materials. As there is currently no secure supply of Sc, several projects worldwide evaluate potential Sc sources. While elsewhere in Europe emphasis is placed upon secondary resources such as red mud, we investigated the potential of industrial garnet sand and its waste products. Since Sc readily substitutes for Mg and Fe in the crystal lattice of garnet, the garnet minerals almandine and pyrope, in particular, may show high Sc concentrations. Garnet sand, after being used as an abrasive in the cutting and sandblasting industry, is recycled several times before it is finally considered waste which eventually must be disposed of. Extraction of Sc (and rare earth elements, REE) from such garnet sand may generate added value and thereby reduce disposal cost. The studied garnet sands from different mines in Australia, India and the U.S., and industrial garnet sands commercially available in Germany from different suppliers show average Sc concentrations of 93.7 mg/kg and 90.7 mg/kg, respectively, i.e. similar to red mud. Our data also show that "fresh" and recycled garnet sands yield similar Sc concentrations. Within the framework of a minimum-waste approach, it may be feasible to utilize the industrial waste-product "garnet sand" as an unconventional source of Sc and REE, that reduces disposal cost.

Anthropogenic gadolinium in tap water and in tap water-based beverages from fast-food franchises in six major cities in Germany.

Gadolinium-based contrast agents used in magnetic resonance imaging are difficult to impossible to remove in wastewater treatment plants, and may enter groundwater production wells and hence municipal tap water via bank filtration. As anthropogenic gadolinium (Gd) may be accompanied by other, more harmful waste water-derived (micro)pollutants such as endocrine disruptors, we investigated the potential pathway of anthropogenic Gd into popular tap water-based beverages sold in highly frequented fast food restaurants. We, therefore, determined the concentration and distribution of geogenic and anthropogenic rare earth elements (REE) in tap water and in a related tap water-based popular soft drink (Coca Cola) from two fast food franchises (McDonalds and Burger King) in six major German cities. We observed anthropogenic Gd in both tap water and corresponding soft drinks in all investigated cities, extending the database for anthropogenic Gd in tap waters and highlighting its widespread distribution. In Berlin and Düsseldorf, where tap water is (mainly) produced by river bank filtration, 85 to 99% of the total Gd is of anthropogenic origin. The surprisingly high anthropogenic fraction (91%) in tap water from Munich reveals that even the shallow groundwater tapped in two Alpine valleys is eventually exposed to anthropogenic pollution. The REE distribution in post-mix soft drinks generally follows that of the corresponding tap water, except for enrichments of ytterbium (Yb), lutetium (Lu) and cerium (Ce), which are derived from the syrup. The concentration of anthropogenic Gd is similar in the soft drinks and in the corresponding tap water, demonstrating that the highly stable Gd-based contrast agents are not removed in soda fountains but are directly transferred to the beverages. This study highlights a pathway for anthropogenic waste water-derived xenobiotics such as pharmaceuticals and endocrine disruptors into the food chain, and hence, reveals the potential for human exposure to potentially harmful anthropogenic compounds.

Strategies for the Synthesis of Chiral Carbon-Bridged Group†IV ansa-Metallocenes.

This minireview provides a survey of the various synthetic approaches to chiral ansa-metallocenes of Ti, Zr, and Hf containing a carbon-based bridge. The individual strategies to install substitution patterns at either the cyclopentadienyl framework or the bridging unit are highlighted with focus on the progress made towards a direct preparation of single complex stereoisomers. The review further includes the discussion of potential problems such as the formation of undesired diastereomers, the threat of racemization of enantiopure material, and synthetic challenges originating from the synthesis, purification, and isolation of the target complexes. The review has been written with the goal in mind to facilitate the design and synthesis of new chiral ansa-metallocene derivatives for emerging research areas in asymmetric catalysis and organometallic chemistry.

A Unified Approach to Customized Chiral Carbon-Bridged ansa-Metallocenes.

Chiral ansa-metallocenes are privileged catalysts for a range of stereoselective transformations. Their synthesis, however, has remained a tremendous challenge, which has prevented a broad and systematic exploration for applications in synthesis and catalysis. A modular approach to such ansa-metallocenes that enables a facile modification of the ring substitution and the ligand bridge, as well as the introduction of various core metals, is described. The complexes were formed with good rac-selectivity and could be isolated with high purity. The strength of the approach was demonstrated by the synthesis of several new and previously known complexes, including a unique helical chiral ansa-metallocene. Using a chiral ligand, a moderate central-to-planar chirality transfer was observed.

Oxidative elemental cycling under the low O2 Eoarchean atmosphere.

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth's earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8-3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology.

Rare earth elements in the aragonitic shell of freshwater mussel Corbicula fluminea and the bioavailability of anthropogenic lanthanum, samarium and gadolinium in river water.

High-technology metals - such as the rare earth elements (REE) - have become emerging contaminants in the hydrosphere, yet little is known about their bioavailability. The Rhine River and the Weser River in Germany are two prime examples of rivers that are subjected to anthropogenic REE input. While both rivers carry significant loads of anthropogenic Gd, originating from contrast agents used for magnetic resonance imaging, the Rhine River also carries large amounts of anthropogenic La and lately Sm which are discharged into the river from an industrial point source. Here, we assess the bioavailability of these anthropogenic microcontaminants in these rivers by analyzing the aragonitic shells of the freshwater bivalve Corbicula fluminea. Concentrations of purely geogenic REE in shells of comparable size cover a wide range of about one order of magnitude between different sampling sites. At a given sampling site, geogenic REE concentrations depend on shell size, i.e. mussel age. Although both rivers show large positive Gd anomalies in their dissolved loads, no anomalous enrichment of Gd relative to the geogenic REE can be observed in any of the analyzed shells. This indicates that the speciations of geogenic and anthropogenic Gd in the river water differ from each other and that the geogenic, but not the anthropogenic Gd is incorporated into the shells. In contrast, all shells sampled at sites downstream of the industrial point source of anthropogenic La and Sm in the Rhine River show positive La and Sm anomalies, revealing that these anthropogenic REE are bioavailable. Only little is known about the effects of long-term exposure to dissolved REE and their general ecotoxicity, but considering that anthropogenic Gd and even La have already been identified in German tap water and that anthropogenic La and Sm are bioavailable, this should be monitored and investigated further.

Importance of nanoparticles and colloids from volcanic ash for riverine transport of trace elements to the ocean: evidence from glacial-fed rivers after the 2010 eruption of Eyjafjallajökull Volcano, Iceland.

Volcanic ashes are often referenced as examples for natural nanoparticles, yet the particle size distribution <1000 nm is only rarely documented. We here report results of a geochemical study of glacial-fed rivers, glacial surface runoff, glacial base flow, and pure glacial meltwater from southern Iceland, that had been sampled 25 days after the explosive eruptions at Eyjafjallajökull in 2010. In addition to the dissolved concentrations of rare earth elements (REE), Zr, Hf, Nb, and Th in the 450 nm-filtered waters, we also studied the respective filter residues (river particulates >450 nm) and volcanic ash. In spite of the low solubilities and high particle-reactivities of the elements studied, most water samples show high dissolved concentrations, such as up to 971 ng/kg of Ce and 501 ng/kg of Zr. Except for the pure glacial meltwater and glacial base flow, all waters display the same shale-normalized REE patterns with pronounced light and heavy REE depletion and positive Eu anomalies. While such patterns are unusual for river waters, they are similar to those of the respective river particulates and the volcanic ash, though at different concentration levels. The distribution of dissolved Zr, Hf, Nb, and Th in the waters also matches that of filter residues and ash. This strongly suggests that in all 450 nm-filtered river waters, the elements studied are associated with solid ash particles smaller than 450 nm. This reveals that volcanic ash-derived nanoparticles and colloids are present in these glacial-fed rivers and that such ultrafine particles control the trace element distribution in the surface runoff. Subsequent to explosive volcanic eruptions, these waters provide terrigenous input from landmasses to estuaries, that is characterized by a unique trace element signature and that subsequent to modification by estuarine processes delivers a pulse of nutrients to coastal seawater in regions not affected by plume fall-out.

Atmospheric oxygenation three billion years ago.

It is widely assumed that atmospheric oxygen concentrations remained persistently low (less than 10(-5) times present levels) for about the first 2 billion years of Earth's history. The first long-term oxygenation of the atmosphere is thought to have taken place around 2.3 billion years ago, during the Great Oxidation Event. Geochemical indications of transient atmospheric oxygenation, however, date back to 2.6-2.7 billion years ago. Here we examine the distribution of chromium isotopes and redox-sensitive metals in the approximately 3-billion-year-old Nsuze palaeosol and in the near-contemporaneous Ijzermyn iron formation from the Pongola Supergroup, South Africa. We find extensive mobilization of redox-sensitive elements through oxidative weathering. Furthermore, using our data we compute a best minimum estimate for atmospheric oxygen concentrations at that time of 3 × 10(-4) times present levels. Overall, our findings suggest that there were appreciable levels of atmospheric oxygen about 3 billion years ago, more than 600 million years before the Great Oxidation Event and some 300-400 million years earlier than previous indications for Earth surface oxygenation.

Rare earth elements in the Rhine River, Germany: first case of anthropogenic lanthanum as a dissolved microcontaminant in the hydrosphere.

The distribution of dissolved rare earth elements (REE) in the Rhine River, Germany, shows the anthropogenic gadolinium (Gd) microcontamination that is commonly observed in rivers in densely populated countries with a highly evolved health care system. However, the Rhine River also carries anomalously high concentrations of lanthanum (La), which produce very large positive La anomalies in normalized REE distribution patterns. These positive La anomalies first occur north of the City of Worms and then decrease in size downstream, but are still significant approximately 400 km downstream, close to the German-Dutch border. The strong La enrichment is of anthropogenic origin and can be traced back to effluent from a production plant for fluid catalytic cracking catalysts at Rhine river-km 447.4. This effluent is characterized by extremely high dissolved total REE and La concentrations of up to 52 mg/kg and 49 mg/kg, respectively. Such La concentrations are well-above those at which ecotoxicological effects have been observed. The Rhine River is the first case observed to date, where a river's dissolved REE inventory is affected and even dominated by anthropogenic La. Our results suggest that almost 1.5t of anthropogenic dissolved La is exported via the Rhine River into the North Sea per year. This reveals that the growing industrial use of REE (and other formerly "exotic" elements) results in their increasing release into the environment, and highlights the urgent need to determine their geogenic background concentrations in terrestrial surface waters.