Situationsbeschreibung bezüglich der Einhaltung der Schwermetallverbote der Batterieverordnung zu
erhalten. Nach geltenden Vorschriften dürfen die Gehalte folgende Grenzwerte nicht überschreiten:
5 ppm Quecksilber (Hg; Knopfzellen: 20000 ppm Hg), 250 ppm Cadmium (Cd) und 4000 ppm Blei
(Pb).
Dazu wurden Mignon-Zellen (Alkali-Mangan, Zink-Kohle), Monozellen (Alkali-Mangan, Zink-Kohle),
Knopfzellen verschiedener chemischer Systeme (Alkali-Mangan, Zink-Luft, Lithium, Silberoxid),
eingebaute Batterien (herausnehmbar und fest eingebaut) von unterschiedlichen Herstellern aus
unterschiedlichen Orten sowie Bezugsquellen auf ihren Gehalt an Cadmium, Blei und Quecksilber
untersucht. Von jedem Batterietyp wurden zwei Exemplare, insgesamt 310 Proben analysiert. Anhand
eines Probenahmeplans wurden Batterien in vier Regionen Deutschlands im Einzelhandel, bei
Straßenhändlern sowie auf Flohmärkten und im Versandhandel käuflich erworben.
Für Rundzellen (Alkali-Mangan, Zink-Kohle) sowie Knopfzellen (Zink-Luft, Lithium, Silberoxid, Alkali-
Mangan) wurden unterschiedliche Analysenstrategien entwickelt. So wurden die Knopfzellen nach
Möglichkeit komplett gelöst und analysiert, bei den Rundzellen kam nur eine mechanische Zerlegung
mit anschließender Analyse von Teilproben in Frage. Die Knopfzellen sowie die Teilproben der
Rundzellen wurden mit Hilfe eines Säureaufschlusses mit Mikrowelle gelöst, zur Bestimmung der
Elemente wurden abhängig vom Gehalt ICP-MS, ICP OES sowie ein automatischer
Quecksilberanalysator verwendet, einzelne unlösliche Graphitteile aus Zink-Kohle Batterien wurden
mit direkter Feststoff-ICP OES analysiert.
Als Ergebnis der Studie wurde erhalten, dass nur in zwei von 155 untersuchten Batterietypen der
Gehalt an Quecksilber leicht oberhalb des Grenzwertes von 2 % lag, für Blei und Cadmium wurden
keine Grenzwertüberschreitungen festgestellt. Bei den beiden Batterien, bei denen eine
Grenzwertüberschreitung vorlag, handelte es sich um Zink-Luft-Knopfzellen, die vom Hersteller als Hgfrei
deklariert waren. Unterschiede nach Bezugsort von Batterien desselben Typs und Herstellers bzw.
nach verschiedenen Größen von Batterien desselben chemischen Systems eines Herstellers konnten
nicht gefunden werden.
The aim of the project was to describe the situation concerning the compliance with the existing
limits for heavy metal content in commercially available batteries in Germany on the basis of a
representative sample. The allowed limits which not have to be exceeded are: 5 ppm of mercury (Hg;
button cells: 20000 ppm Hg), 250 ppm of cadmium (Cd) and 4000 ppm of lead (Pb).
Several batteries of different size such as AA batteries (alkaline/manganese, zinc/carbon), D
batteries (alkaline/manganese, zinc/carbon) and button cells of different chemical systems (zinc-air;
lithium; alkaline/manganese, silver oxide) were analysed for cadmium, lead and mercury. The test
batteries came from different producers and were bought on different places in Germany. From each
battery type two specimen were investigated, in total 294 samples. Following a sampling plan the
batteries were purchased in four regions in Germany by retail, by mail order or on flew markets.
Different strategies for the analysis of AA and D batteries (alkaline/manganese, zinc/carbon) and
for button cells (alkaline/manganese, zinc-air, lithium, silver oxide) were developed. Button cells were
dissolved completely whenever possible. From the bigger types only subspecimens were analysed
after mechanical destruction. Button cells and the subspecimens of the bigger batteries were
decomposed with acid in a microwave oven. For the analysis of the heavy metals ICP-MS, ICP OES
and an automatic mercury analyser were used depending on the content of the interesting element.
Some graphite parts from zinc/carbon batteries were analysed using solid sampling ICP OES.
The result of the study was that only two of 147 batteries had Hg-contents slightly higher than the
limit of 2 %. Pb- and Cd-contents were below the limits for all batteries investigated. The two
batteries with higher Hg-contents were both zinc-air button cells declared by the manufacturer to be
mercury-free. Differences between batteries of the same kind and producer purchased at different
places or between batteries of different size but same producer and same chemical system could not
be detected.
The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.
Ziel des Projekts „Überprüfung der Quecksilber-, Cadmium- und Blei-Gehalte in Batterien. Analyse von Proben handelsüblicher Batterien und in Geräten verkaufter Batterien. Erstellung eines Probenahmeplans, Probenbeschaffung und Analytik“ war es, über eine gut ausgewählte Stichprobe eine qualitative Situationsbeschreibung bezüglich der potenziellen Belastung des Hausmülls und der Batterie-Verwertungsverfahren durch schwermetallhaltige Batterien zu erhalten. In diesem Zusammenhang wurden die ermittelten Schwermetallgehalte der Batterien mit den Grenzwerten und Kennzeichnungsschwellenwerten des BattG verglichen.
An alternative method for lithium isotope amount ratio analysis based on a combination of high-resolution atomic absorption spectrometry and spectral data analysis by machine learning (ML) is proposed herein. It is based on the well-known isotope shift of approximately 15 pm for the electronic transition 22P←22S at around the wavelength of 670.8 nm, which can be measured by the state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry. For isotope amount ratio analysis, a scalable tree boosting ML algorithm (XGBoost) was employed and calibrated using a set of samples with 6Li isotope amount fractions, ranging from 0.06 to 0.99 mol mol–1, previously determined by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The calibration ML model was validated with two certified reference materials (LSVEC and IRMM-016). The procedure was applied toward the isotope amount ratio determination of a set of stock chemicals (Li2CO3, LiNO3, LiCl, and LiOH) and a BAM candidate reference material NMC111 (LiNi1/3Mn1/3Co1/3O2), a Li-battery cathode material. The results of these determinations were compared with those obtained by MC-ICP-MS and found to be metrologically comparable and compatible. The residual bias was −1.8‰, and the precision obtained ranged from 1.9 to 6.2‰. This precision was sufficient to resolve naturally occurring variations, as demonstrated for samples ranging from approximately −3 to +15‰. To assess its suitability to technical applications, the NMC111 cathode candidate reference material was analyzed using high-resolution continuum source atomic absorption spectrometry with and without matrix purification. The results obtained were metrologically compatible with each other.
The therapeutic dose of lithium (Li) compounds, which are widely used for the treatment of psychiatric and hematologic disorders, is close to its toxic level; therefore, drug monitoring protocols are mandatory. Herein, we propose a fast, simple, and low-cost analytical procedure for the traceable determination of Li concentration in human serum, based on the monitoring of the Li isotope dilution through the partially resolved isotope shift in its electronic transition around 670.80 nm using a commercially available high-resolution continuum source graphite furnace atomic absorption spectrometer. With this technique, serum samples only require acidic digestion before analysis. The procedure requires three measurements—an enriched 6Li spike, a mixture of a certified standard solution and spike, and a mixture of the sample and spike with a nominal 7Li/6Li ratio of 0.82. Lanthanum has been used as an internal spectral standard for wavelength correction. The spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Both the spectral constants and the correlation between isotope ratio and relative band intensity have been experimentally obtained using commercially available materials enriched with Li isotopes. The Li characteristic mass (mc) obtained corresponds to 0.6 pg. The procedure has been validated using five human serum certified reference materials. The results are metrologically comparable and compatible to the certified values. The measurement uncertainties are comparable to those obtained by the more complex and expensive technique, isotope dilution mass spectrometry.