Tracking the Flow of Resources in Electronic Waste - The Case of End-of-Life Computer Hard Disk Drives.

Recovery of resources, in particular, metals, from waste flows is widely seen as a prioritized option to reduce their potential supply constraints in the future. The current waste electrical and electronic equipment (WEEE) treatment system is more focused on bulk metals, where the recycling rate of specialty metals, such as rare earths, is negligible compared to their increasing use in modern products, such as electronics. This study investigates the challenges in recovering these resources in the existing WEEE treatment system. It is illustrated by following the material flows of resources in a conventional WEEE treatment plant in Denmark. Computer hard disk drives (HDDs) containing neodymium-iron-boron (NdFeB) magnets were selected as the case product for this experiment. The resulting output fractions were tracked until their final treatment in order to estimate the recovery potential of rare earth elements (REEs) and other resources contained in HDDs. The results further show that out of the 244 kg of HDDs treated, 212 kg comprising mainly of aluminum and steel can be finally recovered from the metallurgic process. The results further demonstrate the complete loss of REEs in the existing shredding-based WEEE treatment processes. Dismantling and separate processing of NdFeB magnets from their end-use products can be a more preferred option over shredding. However, it remains a technological and logistic challenge for the existing system.

Trace element variations in mussels' shells from continent to sea: The St. Lawrence system, Canada.

Rare Earth Elements (REE) and several trace elements abundances in mussel's shells collected along the St. Lawrence River, the Estuary, and the Gulf of St. Lawrence (EGSL) reveal coherent chemical variations, with a sharp contrast between freshwater and seawater bivalves. In freshwater mussel's shells, Rare Earth Elements and Y (REY) patterns are rather flat. Their Mn and Ba concentrations are higher than those of EGSL mussel shells, which are much richer in Sr. Shale-normalized REY abundances in mussel's shells from the EGSL show positive anomalies in La and Y and well-marked negative anomalies in Ce, reflecting those of seawater. Prince Edward Island shells show light REE depletion relative to PAAS, positive La and Y anomalies, and negative Ce anomalies. Our data confirm the lack of detectable Gd pollution in the St. Lawrence River and in the EGSL, as well as Pb pollution at the mouth of the Saguenay Fjord and near Rimouski.

Analysis of flame retardants and elements of concern in printed wiring boards with respect to origin and year of construction.

Thirty-one populated printed wiring boards, covering a range of 30 years of construction, and originating from various electronic devices, were investigated using different analytical procedures. Noble, precious and rare metals, as well as environmentally relevant elements were identified by EDXRF, and lead and the flame retardant (FR) indicator bromine were localised by means of microbeam EDXRF. A GC/MS procedure was developed to identify and quantify FR substances. Several sample preparation techniques were applied, optimised and compared. The method of first choice was ultrasonic extraction because it provided the best compromise between effort, cost and quality of the analytical results. Altogether, a wide variety of elements of concern, and halogenated and phosphate-based FRs were found in the investigated boards. Their occurrence is partially related to the origin and/or year of construction.

Polymer monolithic capillary microextraction combined on-line with inductively coupled plasma MS for the determination of trace rare earth elements in biological samples.

A rapid and sensitive method based on polymer monolithic capillary microextraction combined on-line with microconcentric nebulization inductively coupled plasma MS has been developed for the determination of trace/ultratrace rare earth elements in biological samples. For this purpose, the iminodiacetic acid modified poly(glycidyl methacrylate-trimethylolpropane trimethacrylate) monolithic capillary was prepared and characterized by SEM and FTIR spectroscopy. Factors affecting the extraction efficiency, such as sample pH, sample flow rate, sample/eluent volume, and coexisting ions were investigated in detail. Under the optimal conditions, the LODs for rare earth elements were in the range of 0.08 (Er) to 0.97 ng/L (Nd) with a sampling frequency of 8.5 h(-1), and the RSDs were between 1.5% (Sm) and 7.4% (Nd) (c = 20 ng/L, n = 7). The proposed method was successfully applied to the analysis of trace/ultratrace rare earth elements in human urine and serum samples, and the recoveries for the spiked samples were in the range of 82-105%. The developed method was simple, rapid, sensitive, and favorable for the analysis of trace/ultratrace rare earth elements in biological samples with limited sample volume.

Biomonitoring of rare earth elements in Southern Norway: Distribution, fractionation, and accumulation patterns in the marine bivalves Mytilus spp. and Tapes spp.

Growing extraction and usage of rare earth elements and yttrium (REY) for medical and industrial applications has resulted in increased discharges into the marine environment. Using Mytilus spp. Mussels and Tapes spp. clams as bioindicator organisms, we analyzed 15 REY in soft tissues of specimens collected at two potentially polluted sites in Southern Norway: in the vicinity of an industry producing gadolinium-based MRI contrast agents (GBCAs) (Lindesnes) and in an industrially-affected fjord (Porsgrunn). The spatial distribution of REY and shale-normalized fractionation patterns were determined to assess the potential anthropogenic contribution of REY at the sites. At both sites, the REY fractionation pattern in soft tissue was characterized by enrichment of light rare earth elements (LREE) over heavy rare earth elements (HREE), while also displaying negative cerium and small positive gadolinium (Gd) anomalies. LREEs contributed to over 80% of the total REY concentrations, with increasing relative enrichment following higher total REY. Gd anomalies remained conserved in most sites despite significant differences in total REY; however, a high Gd anomaly (Gd/Gd* = 4.4) was found downstream of the GBCA industry spillwater outlet, indicating biotic uptake of excess anthropogenic Gd at this site. Total REY concentrations in clams in Porsgrunn were one order of magnitude higher than in mussels in Lindesnes. This may be attributable to freshwater influences in Porsgrunn, where clams collected closer to the river mouth had significantly higher total REY concentrations. This study constitutes the first assessment of REY concentrations in marine bivalves in Norway and can provide useful information for future biomonitoring studies on REY contamination.

The distribution and enrichment of trace elements in surface and core sediments from the Changjiang River Estuary, China: Evidence for anthropogenic inputs and enhanced availability of rare earth elements (REE).

Huge amount of trace metals emitted through manmade activities are carried by the Changjiang River into the East China Sea. Most of them deposit in the Changjiang River Estuary and threaten the regional aquatic environment. In this study, major and trace elements of 34 archive surface sediments and two cores are examined. Sequential extraction procedures were also performed on surface sediments from 12 sites. We found that Tl, Tm, Er show distinct accumulation in surface sediments in the order of Tm > Tl > Er. Particularly, abnormally elevated HREE are observed mainly in those sites near the mouth of the estuary. Most elements exhibit an obvious reduction in the upper 30 cm of core B8, reflecting a decrease of sediment discharge from Changjiang River runoff. The increase of some trace elements recorded in the upper 20 cm of core C3 demonstrates a distinct local anthropogenic input in recent years.

Role of intrinsic physicochemical parameters on multi-element distribution in surface sediment of the Devi River estuary, eastern India.

Multi-element composition including rare earth elements (REE) of surface sediment from the Devi river estuary, eastern coast of India, have been analysed in order to study the weathering characteristics and provenance of sediment along with their behaviour under different physicochemical conditions. These sediments with dominantly felsic provenance have undergone low to moderate chemical alterations. Bulk chemical composition is mainly represented by SiO2, Al2O3, Fe2O3 and K2O. Concentrations of Ba, Nb, Pb, Rb, Th and Zr are above their respective upper crustal abundances. High LREE/HREE ratio, negative Eu anomalies, and (La/Yb)n and (Tb/Yb)n values confirm that sediments are dominantly derived from the Eastern Ghat Group of rocks. Upper estuary sediments show negative Eu anomalies which is similar to that of the source. However, positive Eu anomaly is mostly observed in lower estuary. Contrasting Eu anomalies between upper- and lower-estuarine sediments are uncharacteristic of previously studied major global estuaries. Strong negative correlation between Mn and Eu suggests control of redox conditions over distribution of Eu. Concentration of REEs, Sc, Fe, Mo, V, Zn, Zr, Nb, U, Ti, Na and P increases up to 20 ppt salinity, and followed by declining trend towards mouth. This is mostly due to removal through flocculation of colloidal particles from water column during fresh- and saline-water interaction. This could be the first report about coagulation-based behaviour of Mo in estuarine environment. There is gradual decline in concentration of Cr, Co, Ni, Cu, Rb, Sr, Sb, Cs, Ba, Pb, Al, Mn, Mg, Ca and K with increase in salinity which is attributed to saline induced desorption of elements from sediments. The SiO2 content shows increasing trend towards mouth. Findings of this study highlight the importance of intrinsic physicochemical parameters, mainly salinity and redox condition, on governing geochemical behaviour of different elements including REE in mangrove dominated estuarine sediment.

Baseline on rare earth elements in the marine sediments of a Mediterranean commercial port as environmental tracers and their relationships with inorganic contaminants.

The Port of Genoa (north-western Mediterranean Sea) receives sediments from two different catchment areas (Bisagno and Polcevera torrents). The aim of the work is to evaluate if Rare Earth Elements (REEs) could be used to identify the two sedimentary inputs and to unravel the origin of inorganic contaminants in an anthropised basin. REE results constitute a baseline for this port. The main REE-bearing minerals are phosphates and zircon. As, Cd, Hg, Pb, and Sn concentrate in the sediments closer to the Bisagno Torrent mouth, and the correlation with Ca and Light-REEs suggests their plausible geological origin. Co, Mn, and Ni maxima lie in the sediments closer to the Polcevera Torrent. Their correlation with Middle-REEs and Mg suggest that ophiolitic rocks could explain their presence. Cr, Cu, V, and Zn do not show a clear correlation with REEs, and their origin probably is a combination of natural and anthropogenic sources.

Removal of magnetic resonance imaging contrast agents through advanced water treatment plants.

Stable gadolinium (Gd) complexes have been used as paramagnetic contrast agents for magnetic resonance imaging (MRI) for over 20 years, and have recently been identified as environmental contaminants. As the rare earth elements (REE), which include Gd, are able to be measured accurately at very low concentrations (e.g. Tb is measured at 7 fmol/kg in this study) using inductively coupled plasma mass spectrometry (ICP-MS), it is possible to determine the fate of this class of compounds during the production of purified recycled water from effluent. Coagulation and microfiltration have negligible removal, with the major removal step occurring across the reverse osmosis membrane where anthropogenic Gd (the amount of Gd attributable to MRI contrast agents) is reduced from 0.39 nmol/kg to 0.59 pmol/kg, a reduction of 99.85%. The RO concentrate has anthropogenic Gd concentrations of 2.6 nmol/kg, an increase in concentration in line with the design characteristics of the plant. The increased concentration in the RO concentrate may allow further development of anthropogenic Gd as a tracer of the fate of the RO concentrate in the environment.

Species and distribution of rare earth elements in the Baotou section of the Yellow River in China.

This paper analyses the contents and species distributions of rare earth elements (REEs) in the water-suspended particulate-sediment system of the Baotou section of the Yellow River, China, with known anthropogenic REE input from industrial discharges. The major forms of REEs were suspended and dissolved in the mainstream and the tributaries of the Baotou section, respectively. The concentrations of the dissolved and suspended REEs had the same trends in the overlying water along the mainstream, which increased from the Seqi section (site A) to the mouth of the Sidaosha River (site D), reaching a maximum value at site D, and tending to decrease thereafter. The contents of REEs in sediment cores showed enrichment with light rare earth elements (LREEs). The bound to carbonates and to Fe-Mn oxides are the major forms of REE in the secondary phase and the REE exhibited LREE enrichment pattern and moderate Eu depletion in suspended particulates and surface sediments. The contents and species distributions of REEs in the water-suspended particulate-sediment system of the Baotou section suggest that the anthropogenic source of REEs from Baotou city have enhanced REE accumulation to the Baotou section. This information is important for predicting possible pollution resulting from anthropogenic REE input into rivers.

Application of rare earth-doped nanoparticles in biological imaging and tumor treatment.

Rare earth-doped nanoparticles have been widely used in disease diagnosis, drug delivery, tumor therapy, and bioimaging. Among various bioimaging methods, the fluorescence imaging technology based on the rare earth-doped nanoparticles can visually display the cell activity and lesion evolution in living animals, which is a powerful tool in biological technology and has being widely applied in medical and biological fields. Especially in the band of near infrared (700-1700 nm), the emissions show the characteristics of deep penetration due to low absorption, low photon scattering, and low autofluorescence interference. Furthermore, the rare earth-doped nanoparticles can be endowed with the water solubility, biocompatibility, drug-loading ability, and the targeting ability for different tumors by surface functionalization. This confirms its potential in the cancer diagnosis and treatment. In this review, we summarized the recent progress in the application of rare earth-doped nanoparticles in the field of bioimaging and tumor treatment. The luminescent mechanism, properties, and structure design were also discussed.

Influence of winemaking practices on the concentration of rare earth elements in white wines studied by inductively coupled plasma mass spectrometry.

Influence of clarification, filtration, and storage on the concentration of rare earth elements (REEs) was studied in white wines by inductively coupled plasma mass spectrometry (ICP-MS). Smooth and parallel chondrite-normalized (CN) plots were obtained for wines which have never been in contact with fining agents. Clarification and filtration generally used in white wine production were simulated in the laboratory using nontreated reference wines, and CN plots were compared before and after treatments. Clarification by bentonites yields an overall increase in REE concentrations resulting in substantially parallel CN curves well above the plots of the corresponding nontreated wines. Filtration using silicate (SiO2), on the other hand, changes the CN profile in a nonparallel manner due to a higher release of La, Ce, Pr, Nd, and Gd, more than other elements studied. Filtration with cellulose powder causes a small increase in the concentration of light REEs, while the concentrations of other elements remain basically unchanged. Storage conditions could also affect the REE pattern of wine. We found that the influence of glass is greater than that of stainless steel and wood. In addition, we report that commercially available finished white wines from the same region show highly different REE patterns depending on the winemaking practices employed.

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

Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due to the unclear atmospheric signature of these elements and their adverse impact on human health and the environment. In this study, ambient particulate matter of different sizes was collected from one site in an integrated iron and steelmaking industrial zone (HG) and one urban background site with no direct industrial emissions (ZWY) during a 1-year sampling campaign in China. The total concentrations of REEs for TSP, PM10, and PM2.5 were 27.248, 14.989, 3.542 ng/m(3) in HG and 6.326, 5.274, 1.731 ng/m(3), respectively, in ZWY, which revealed the local influence of the steelmaking activities to the air quality. With respect to ZWY, the REEs in HG site are obviously fractionated in the coarser fraction, and LREEs account for more than 80 % of the total REE burden in all of the samples. Additionally, the REEs in HG and ZWY show a homogeneous trend with successively increased LREE/HREE ratios from the coarse particles to the fine particles. In our samples, La, Ce, Nd, and Sm are the most enriched rare earth elements, especially in the HG site. Moreover, ternary diagrams of LaCeSm indicate that the REEs in HG are potentially contributed by steelworks, carrier vehicles, coal combustion, and road dust re-suspension.

Characterization of MBa2Cu3O7-x thin films by Raman microspectroscopy.

Thin film embodiments of MBa2Cu3O7-x (MBCO, M = yttrium or a rare-earth metal) prepared by several different deposition methods on a variety of substrates were investigated by Raman microspectroscopy. Several of the unique characterization capabilities of Raman spectroscopy in the analysis of MBCO thin films are highlighted by the results of these investigations. The Raman active phonons of the orthorhombic and tetragonal forms of MBCO that are most useful for characterization of textured MBCO films are diagrammed and discussed. A rapid procedure for qualitative texture mapping of MBCO thin films using Raman microscopy techniques is presented, and a new approach for investigating phase separation at the sub-micrometer level in MBCO thin films based on curve resolution of the MBCO Cu2 phonon is described. The assignment of a particular feature often observed in Raman spectra of MBCO films to cation disorder is reinforced by results of a cation substitution study. The depth of penetration of the laser into MBCO films and the type of information that can be obtained by varying the extent of defocusing of the laser are also discussed.

Separation and determination of rare earth elements by Dowex 2-X8 resin using sodium trimetaphosphate as elution agent.

The distribution coefficients of rare earth elements and thorium with Dowex 2-X8, 200-400 mesh, a strongly basic anion-exchange resin, have been determined regarding four different concentrations of sodium trimetaphosphate (3 x 10(-3), 5 x 10(-3), 7 x 10(-3) and 0.01 M). The separation of the rare earths and thorium obtained from an Australian monazite has been investigated by anion-exchange chromatography with sodium trimetaphosphate concentration gradient on a Dowex 2-X8 ion-exchange columns. The order of elution of the elements was the reverse of the order of elution of the same elements on Dowex 1 resin. The elution was investigated using 5 mg and 250 mg samples. In the separation of 5 mg samples, all elements were separated in 29 min. It has been seen that the elution peaks are narrow, tailing effects are very small, Dy and Y are well separated. Qualitative and quantitative determinations were realized by spectrofluorometry.

[Determination of rare-earth and trace elements in teeth enamel by inductively coupled plasma mass spectroscopy].

Determination of rare earth and trace elements in teeth enamel was studied by inductively coupled plasma mass spectroscopy. The sample was completely dissolved by HNO3-H2O2. The range of precision is 0.50%-6.79% given by the relative standard deviation and the range of accuracy is 94.45%-104.78% obtained by measuring standard recovery rate. The above data satisfied completely the requirements of biological sample. While this study provides experimental data of rareearth and trace elements of teeth enamel for carious teeth and none carious teeth of human for prevention and cure of decayed tooth. A reasonable method is provided for mouth medicine research.

In vitro biocompatibility and endothelialization of novel magnesium-rare Earth alloys for improved stent applications.

Magnesium (Mg) based alloys are the most advanced cardiovascular stent materials. This new generation of stent scaffold is currently under clinical evaluation with encouraging outcomes. All these Mg alloys contain a certain amount of rare earth (RE) elements though the exact composition is not yet disclosed. RE alloying can usually enhance the mechanical strength of different metal alloys but their toxicity might be an issue for medical applications. It is still unclear how RE elements will affect the magnesium (Mg) alloys intended for stent materials as a whole. In this study, we evaluated MgZnCaY-1RE, MgZnCaY-2RE, MgYZr-1RE, and MgZnYZr-1RE alloys for cardiovascular stents applications regarding their mechanical strength, corrosion resistance, hemolysis, platelet adhesion/activation, and endothelial biocompatibility. The mechanical properties of all alloys were significantly improved. Potentiodynamic polarization showed that the corrosion resistance of four alloys was at least 3-10 times higher than that of pure Mg control. Hemolysis test revealed that all the materials were non-hemolytic while little to moderate platelet adhesion was found on all materials surface. No significant cytotoxicity was observed in human aorta endothelial cells cultured with magnesium alloy extract solution for up to seven days. Direct endothelialization test showed that all the alloys possess significantly better capability to sustain endothelial cell attachment and growth. The results demonstrated the promising potential of these alloys for stent material applications in the future.

Enrichment of rare earth elements as environmental tracers of contamination by acid mine drainage in salt marshes: a new perspective.

Rare earth elements (REE) were analyzed in surface sediments from the Guadiana Estuary (SW Iberian Pyrite Belt). NASC (North American Shale Composite) normalized REE patterns show clearly convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE, indicating acid-mixing processes between fluvial waters affected by acid mine drainage (AMD) and seawater. However, REE distributions in the mouth (closer to the coastal area) show slightly LREE-enriched and flat patterns, indicating saline-mixing processes typical of the coastal zone. NASC-normalized ratios (La/Gd and La/Yb) do not discriminate between both mixing processes in the estuary. Instead, a new parameter (E(MREE)) has been applied to measure the curvature in the MREE segment. The values of E(MREE)>0 are indicative of acid signatures and their spatial distribution reveal the existence of two decantation zones from flocculation processes related to drought periods and flood events. Studying REE fractionation through the E(MREE) may serve as a good proxy for AMD-pollution in estuarine environments in relation to the traditional methods.

Addition of tracers into the polypropylene in view of automatic sorting of plastic wastes using X-ray fluorescence spectrometry.

This study focused on the detection of rare earth oxides, used as tracers for the identification of polymer materials, using XRF (X-ray fluorescence) spectrometry. The tests were carried out in a test system device which allows the collection of static measurements of the samples' spectrum through the use of energy dispersive X-ray fluorescence technology. A sorting process based on tracers added into the polymer matrix is proposed in order to increase sorting selectivity of polypropylene during end-of-life recycling. Tracers consist of systems formed by one or by several substances dispersed into a material, to add a selective property to it, with the aim of improving the efficiency of sorting and high speed identification. Several samples containing rare earth oxides (Y(2)O(3), CeO(2), Nd(2)O(3), Gd(2)O(3), Dy(2)O(3), Er(2)O(3) and Yb(2)O(3)) in different concentrations were prepared in order to analyse some of the parameters which can influence the detection, such as the concentration of tracers, the acquisition time and the possible overlapping among the tracers. This work shows that by using the XRF test system device, it was possible to detect 5 of the 7 tracers tested for 1min exposure time and at a concentration level of 1000ppm. These two parameters will play an important role in the development of an industrial device, which indicates the necessity of further works that needs to be conducted in order to reduce them.

Uphill transport of rare-earth metals through a highly stable supported liquid membrane based on an ionic liquid.

We have developed a highly stable supported liquid membrane based on ionic liquids (ILs) for the separation of rare-earth metals, employing N,N-dioctyldiglycol amic acid as a mobile carrier. The quantitative transport of Y and Eu through the membrane was successfully attained, and separation from metal impurities, Zn, was efficiently accomplished. A membrane stable enough for long-term operation was constructible from imidazolium-based ILs having a longer alkyl chain, such as octyl or dodecyl groups in an imidazolium cation.