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- Battery (2)
- Button cell (2)
- Cadmium (2)
- Determination of heavy metals (2)
- Lead (2)
- Lithium (2)
- Mercury (2)
- Silver oxide (2)
- Zinc-air (2)
- Zinc/Carbon (2)
Within the framework of a German government project (initiated by the Federal Environment Agency) to check the compliance of commercially available batteries with the German Battery Ordinance concerning their heavy metal contents, 18 different types of commercially available zinc-air button cells were analysed for their cadmium, lead and mercury contents. After microwave assisted dissolution with aqua regia, Cd and Pb were determined using inductively coupled plasma mass spectrometry (ICP-MS), and Hg was determined using inductively coupled plasma optical emission spectrometry (ICP OES) and atomic absorption spectrometry. Cd contents were found to be much lower than the permitted limits; Pb contents were also found to be below the limits. Hg contents were found to be near the limits, and in one case the limit was exceeded.
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.
A first pilot study on the sorption of environmental pollutants on various microplastic materials
(2017)
With the drastic increase in plastic production, the input of plastic particles into the environment has become a recognised problem.
Xenobiotics are able to sorb to polymer materials, and this process is further enhanced where they Encounter microplastics (plastic fragments <5 mm). In this work we studied the sorption of metformin, a type-2 diabetes drug, and difenoconazole, a fungicide, onto the virgin polymer materials polyamide (PA), polypropylene (PP), and polystyrene (PS). Additionally, PP was cryo-milled and PA was treated with acid to investigate the influence of an increase in surface area and chemical modification. The material properties were also studied by dynamic scanning calorimetry (DSC), gel permeation chromatography (GPC) and Fourier transform infrared spectroscopy (FTIR). Sorption experiments were performed on the basis of a full factorial design examining the effect of agitation, pH value, and salinity. Experimental results showed that difenoconazole sorbs readily to all microplastics, whereas the more polar analyte metformin did not show any affinity to the materials used. For difenoconazole the governing factor in all cases is agitation, while both pH and salinity exhibited only a slight influence. The modification of polymers leads to enhanced sorption, indicating that an increase in surface area (cryo-milled PP) or inner volume (acid-treated PA) strongly favours adsorption. Moreover, long-term experiments demonstrated that the time until equilibrium is reached depends strongly on the particle size.