Renato Figi

Quantitative analysis of heavy metals in automotive brake linings: A comparison between wet-chemistry based analysis and in-situ screening with a handheld X-ray fluorescence spectrometer

Two extraction procedures for ecologically relevant elements present in automotive brake linings (Sb, Bi, Pb, Cd, Cr (total), Co, Cu, Mo, Ni, Sr, V, Zn, Sn) were developed and validated, applying a high pressure asher (HPA-S) and microwave extraction, respectively. Both of these methods allowed for the quantitative analysis of the extracted elements by inductively coupled plasma optical emission spectrometry (ICP-OES). The results were compared to measurements using a handheld energy-dispersive X-ray fluorescence spectrometer (ED-XRF), being in discussion by regulating agencies as in-situ screening tool for brake pads. The comparison indicates that the handheld ED-XRF analysis is basically an efficient screening tool for a reliable assessment of trace metal contents in automotive brake pads with respect to legal standards. While a quantitative determination of elements like Cd, Co, Cr, Mn, Mo, Ni, Pb and Sb was achievable, other elements (V, Cu, Bi, Zn, Sn and Sr) could only be determined qualitatively due to the special matrix characteristics of brake pads.

A straightforward wet-chemistry method for the determination of solid and gaseous mercury fractions in Backlight Cold Cathode Fluorescence Lamps

Backlight Cold Cathode Fluorescence Lamps (B-CCFLs) are already applied in many electronic consumer products such as LCD screens, flat screen TVs, and laptop monitors. In consequence, an increase of such products entering the waste streams can be expected in the near future. As a result of the mercury (Hg) employed in such lamps, the development of recycling techniques to create a best practical environmental option for appropriate end-of-life strategies are necessary. For this purpose the knowledge about speciation in terms of solid and gaseous state of Hg in such lamps is inevitable. However, analytical techniques to discriminate solid and gaseous Hg require a special setup, not available in most routine laboratories. Thus a straightforward and cost efficient analytical technique is of need. In this work we describe sample preparation procedures and analysis techniques, which only require equipment already available in most routine laboratories. The volatile fraction is extracted with a KMnO(4) solution utilizing a novel approach, taking the advantage that the B-CCFL glass tubes have a negative pressure. Thus the extraction solution is directly sucked into the tube where the volatile Hg-fraction is immediately extracted. Subsequently, the solid fraction is dissolved via microwave assisted pressure acid digestion after cryo-milling. Analysis for both fractions took place employing a cold vapor atomic absorption system. To prove the new method is fit for purpose, spiking experiments and analysis of reference materials (when available) was performed with recoveries being between 90% and 110%. First results obtained for a stack of lamps from an used LCD-TV display reveal that solid Hg fractions in all lamps show a variation of 20% between samples whereas the gaseous Hg content can vary up to 600%.

Refractive indices of layers and optical simulations of Cu(In,Ga)Se2 solar cells

Abstract Cu(In,Ga)Se2 -based solar cells have reached efficiencies close to 23%. Further knowledge-driven improvements require accurate determination of the material properties. Here, we present refractive indices for all layers in Cu(In,Ga)Se2 solar cells with high efficiency. The optical bandgap of Cu(In,Ga)Se2 does not depend on the Cu content in the explored composition range, while the absorption coefficient value is primarily determined by the Cu content. An expression for the absorption spectrum is proposed, with Ga and Cu compositions as parameters. This set of parameters allows accurate device simulations to understand remaining absorption and carrier collection losses and develop strategies to improve performances.

A tough nut to crack: quantitative analysis of heavy metals in automotive brake linings

*Correspondence: C. Ringlia, Tel.: +41 44 634 82 33, E-mail: chringli@botinst.uzh. ch; L. Biglerb, Tel.: +41 44 635 42 86, E-mail: lbigler@oci.uzh.ch aInstitute of Plant Biology, University of Zürich, Zollikerstrasse 107, CH-8008 Zürich bInstitute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich cPresent address: Energy Biosciences Institute, University of Berkeley, CA, USA

Functional lignocellulosic material for the remediation of copper(II) ions from water: Towards the design of a wood filter

In this study, the chemical modification of bulk beech wood is described along with its utilization as biosorbent for the remediation of copper from water. The material was prepared by esterification using anhydrides, and reaction conditions were optimized to propose a greener process, in particular by reducing the amount of solvent. This modification yields a lignocellulosic material whose native structure is preserved, with an increased amount of carboxylic groups (up to 3 mmol/g). We demonstrate that the material can remove up to 95% of copper from low concentration solutions (100- 500 ppm). The adsorption efficiency decreases with concentrated copper solutions, and we show that a limited number of -COOH groups participate in copper binding (ca. 0.1 Cu/-COOH). This result suggests a limited accessibility of -COOH groups in the wood scaffold. This was demonstrated by the characterization of -COOH and copper distributions inside wood. Raman and EDX imaging confirmed that most -COOH groups are located inside the wood cell walls, thereby limiting interactions with copper. According to this study, critical limitations of bulk wood as a biosorbent were identified, and the results will be used to improve the material and design an efficient wood filter for heavy metal remediation.

Differentiation of dental restorative materials combining energy-dispersive X-ray fluorescence spectroscopy and post-mortem CT

Today, post-mortem computed tomography (CT) is routinely used for forensic identification. Mobile energy-dispersive X-ray fluorescence (EDXRF) spectroscopy of a dentition is a method of identification that has the potential to be easier and cheaper than CT, although it cannot be used with every dentition. In challenging cases, combining both techniques could facilitate the process of identification and prove to be advantageous over chemical analyses. Nine dental restorative material brands were analyzed using EDXRF spectroscopy. Their differentiability was assessed by comparing each material’s x-ray fluorescence spectrum and then comparing the spectra to previous research investigating differentiability in CT. To verify EDXRF’s precision and accuracy, select dental specimens underwent comparative electron beam excited x-ray spectroscopy (EDS) scans, while the impact of the restorative surface area was studied by scanning a row of dental specimens with varying restorative surface areas (n = 10). EDXRF was able to differentiate all 36 possible pairs of dental filling materials; however, dual-energy CT was only able to differentiate 33 out of 36. The EDS scans showed correlating x-ray fluorescence peaks on the x-ray spectra compared to our EDXRF. In addition, the surface area showed no influence on the differentiability of the dental filling materials. EDXRF has the potential to facilitate corpse identification by differentiating and comparing restorative materials, providing more information compared to post-mortem CT alone. Despite not being able to explicitly identify a brand without a control sample or database, its fast and mobile use could accelerate daily routines or mass victim identification processes. To achieve this goal, further development of EDXRF scanners for this application and further studies evaluating the method within a specific routine need to be performed.

Effects of potassium on kesterite solar cells: Similarities, differences and synergies with sodium

Addition of alkali dopants is essential for achieving high-efficiency conversion efficiency of thin film solar cells based on chalcogenide semiconductors like Cu(In,Ga)Se2 (CIGS) and Cu2ZnSn(S,Se)4 (CZTSSe also called kesterite). Whereas the treatment with potassium allows boosting the performance of CIGS solar cells as compared to the conventional sodium doping, it is debated if similar effects can be expected for kesterite solar cells. Here the influence of potassium is investigated by introducing the dopant during the solution processing of kesterite absorbers. It is confirmed that the presence of potassium leads to an enhanced grain growth and a ten-fold lower potassium concentration is sufficient for obtaining grain size similar to sodium-containing absorbers. Potassium is located predominantly at grain boundaries and it suppresses incorporation of sodium into the absorber layer. The potassium doping increases the apparent carrier concentration to ∼2×1016 cm-3 for a potassium concentration of 0.2 at%...

Determination of non-gaseous and gaseous mercury fractions in unused fluorescent lamps: A study of different lamp types

Since incandescent light bulbs have been phased out in the European Union from 2009, the use of fluorescent lamps has drastically increased as a reliable, more energy-efficient and cost-effective alternative. State-of-the-art fluorescent lamps are dependent on mercury/mercury alloys, posing a risk for the consumer and the environment, and appropriate waste management is challenging. Consequently analytical methods to determine possible mercury species (non-gaseous/gaseous) in these lamps are of need. Here, a straightforward and wet-chemistry-based analytical strategy for the determination of gaseous and non-gaseous mercury in commercially available fluorescent lamps is presented. It can be adapted in any analytical laboratory, without or with only minimum modifications of already installed equipment. The analytical figures of merit, as well as application of the method to a series of commercially available fluorescent lamps, are presented. Out of 14 analysed and commercially available lamp types, results from this study indicate that only one contains a slightly higher amount of mercury than set by the legislative force. In all new lamps the amount of gaseous mercury is negligible compared with the non-gaseous fraction (88%–99% of total mercury).