Long-Term Monitoring of Palladium and Platinum Contents in Road Dust of the City of Munich, Germany

  • Holger Sievers
  • Michael SchusterEmail author
Part of the Environmental Science and Engineering book series (ESE)


The concentration of platinum group metals (PGM), namely palladium, platinum and rhodium, has increased in all earth spheres, which is mainly due to the worldwide use of automotive catalytic converters containing these metals as active components. Especially high concentrations are therefore found near busy roads and in urban environments where PGM concentrations now have reached a level that has let scientists and engineers think about possibilities to recycle these precious metals in the context of urban mining strategies. Especially palladium has been classified as particularly critical as it shows a comparatively high mobility in environmental compartments and elevated toxicological effects. It is therefore advisable and necessary to monitor traffic related PGM emissions with particular focus on palladium. One way to do this is long-term monitoring of PGM emissions under largely constant conditions. In the present work this has been done by monitoring palladium concentrations in tunnel dust of the outer city ring (B2R) of Munich, Germany. Dust samples were collected from 1994 until 2012 from the roofs of emergency telephone boxes installed in the tunnels Landshuter Allee, Candid and Trappentreu and analyzed for their palladium and some of them for their platinum content. Major and minor matrix components have also been analyzed to ensure comparability of the samples. PGM Analysis was performed with Graphite Furnace Atomic Absorption Spectrometry (GFAAS) after complete sample digestion and enrichment of palladium and platinum with N,N-Dialkyl-N’-benzoylthioureas acting as highly selective chelating agents. Matrix characterization was performed by elementary analysis and Total Reflection X-ray Fluorescence (TXRF). The main matrix components determined in the road dust samples from 1994 to 2012 show, apart from one noteworthy exception (sulfur) a quite constant composition. The sulfur content in the dust samples of all three tunnels decreased significantly in the years after 1998. This is most probably attributable to the legally required reduction of the sulphur content in gasoline and diesel fuels. The average palladium concentration in the dust samples increased significantly from 1994 to 2007 where it reached a maximum. From 2009 onwards there was a steady decline in the average palladium concentration, reaching a minimum in 2012. The increase of the palladium concentration in the tunnel dust from 1994 to 2007 can easily be explained by the gradual replacement of platinum by palladium in automotive catalytic converters. In 2007 traffic density monitored by the municipal administration of the city of Munich also reached a high level which roughly remained the same up to today. Platinum concentration in the dust samples also reached a maximum in 2007 and declined from 2007 to 2012. The most likely explanation for the decline of the palladium and platinum concentration in the tunnel dust after 2007 is progress in the production of automotive catalytic converters and/or progress in automobile engine construction.


Dust Sample Road Dust Cloud Point Extraction Platinum Group Metal Graphite Furnace Atomic Absorption Spectrometry 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


  1. Aberer W, Holub H, Strohal R, Slavicek R (1993) Palladium in dental alloysthe dermatologists’ responsibility to warn? Contact Dermatitis 28:163−165CrossRefGoogle Scholar
  2. Al-Bazi SJ, Chow A (1984) Platinum metals-solution chemistry and separation methods (ion-exchange and solvent extraction). A Chow, Talanta 31:815−836CrossRefGoogle Scholar
  3. Alshanaa U, Aygüna RS (2011) Determination of platinum and palladium in soil as their chelates with N, N-diethyl-N’-benzoylthiourea by RP-HPLC. J Liq Chromatogr Relat Technol 34:14CrossRefGoogle Scholar
  4. Barbante C, Veysseyre A, Ferrari C, Van de Velde K, Morel C, Capodaglio G, Cescon P, Scarponi G, Boutron C (2001) Greenland snow evidence of large scale atmospheric contamination for platinum, palladium, and rhodium. Environ Sci Technol 35:835−839CrossRefGoogle Scholar
  5. Bensch W, Schuster M (1992) Die Kristallstruktur von Tris(N, N-Diethyl-N’-benzoylthioureato)rhodium (III). Z Anorg Allg Chem 615:93CrossRefGoogle Scholar
  6. Boch K, Schuster M, Risse G, Schwarzer M (2002) Microwave-assisted digestion procedure for the determination of palladium in road dust. Anal Chim Acta 459:257−265CrossRefGoogle Scholar
  7. Jackson MT, Sampson J, Prichard HM (2007) Platinum and palladium variations through the urban environment: evidence from 11 sample types from Sheffield. UK Sci Tot Environ 385:117CrossRefGoogle Scholar
  8. Matthey J (2012) Platinum 2012 Interim ReviewGoogle Scholar
  9. König K-H, Schuster M, Schneeweis G, Steinbrech B (1984) Zur Chromatographie von Metallchelaten XIV. Dünnschicht-Chromatographie von N, N-Dialkyl-N’-benzoylthioharnstoff-Chelaten. Fresenius Z Anal Chem 319:66CrossRefGoogle Scholar
  10. König K-H, Schuster M, Steinbrech B, Schneeweis G, Schlodder R (1985) N, N-Dialkyl-N’-benzoylthioharnstoffe als selektive Extraktionsmittel zur Abtrennung und Anreicherung von Platinmetallen. Fresenius Z Anal Chem 321:457CrossRefGoogle Scholar
  11. König K-H, Pletsch H-J, Schuster M (1986) N, N-Dialkyl-N’-benzoylharnstoffe als Fällungs- und Extraktionsreagenzien. Fresenius Z Anal Chem 325:621CrossRefGoogle Scholar
  12. König K-H, Schuster M, Hollmann D, Schlodder R (1988) Verfahren zur Abtrennung und Reinigung der Platingruppenmetalle. EP 144(566):B1Google Scholar
  13. König K-H, Schuster M, Schneeweis G, Steinbrech B, Schlodder R (1987) Verfahren zur Abtrennung und Reinigung der Platingruppenmetalle. EP 144(565):B1Google Scholar
  14. Kristine H, Morrison G, Rach S (2004) Environmental routes for platinum group elements to biological materials—a review. Sci Total Environ 334−335:21−38Google Scholar
  15. Leopold K, Maier M, Weber S, Schuster M (2008) Long-term study of palladium in road tunnel dust and sewage sludge ash. Environ Pollut 156:341−347CrossRefGoogle Scholar
  16. Limbeck A, Rudolph E, Hann S, Koellensperger G, Stingeder G, Rendl J (2004) Flow injection on-line pre-concentration of platinum coupled with electrothermal atomic absorption spectrometry. J Anal At Spectrom 19:1474Google Scholar
  17. Meeravali NN, Jiang S-J (2008) Interference free ultra-trace determination of Pt, Pd and Au in geological and environmental samples by inductively coupled plasma quadrupole mass spectrometry after a cloud point extraction. J Anal At Spectrom 23:854−860CrossRefGoogle Scholar
  18. Philippeit G, Angerer J (2001) Determination of palladium in human urine by high-performance liquid chromatography and ultraviolet detection after ultraviolet photolysis and selective solid-phase extraction. J Chromatogr B Biomed Sci Appl 760:237−245CrossRefGoogle Scholar
  19. Pytlakowska K, Kozik V, Dabioch M (2013) Complex-forming organic ligands in cloud-point extraction of metal ions: a review. Talanta 110:202−228Google Scholar
  20. Rauch S, Hemond HF, Barbante C, Owari M, Morrison GM, Peucker-Ehrenbrink B, Wass U (2005) Importance of automobile exhaust catalyst emissions for the deposition of platinum, palladium, and rhodium in the Northern Hemisphere. Environ Sci Technol 39:8156−8162CrossRefGoogle Scholar
  21. Schäfer J, Hannker D, Eckhardt J-D, Stüben D (1998) Uptake of traffic-related heavy metals and platinum group elements (PGE) by plants. Sci Total Environ 215:59−67CrossRefGoogle Scholar
  22. Schuster M, Unterreitmaier E (1993) Fluorometric detection of heavy metals with pyrene substituted N-acylthioureas. Fresenius J Anal Chem 346:630CrossRefGoogle Scholar
  23. Schuster M, Schwarzer M (1996) Selective determination of palladium by on-line column preconcentration and graphite furnace atomic absorption spectrometry. Anal Chim Acta 328:1CrossRefGoogle Scholar
  24. Schuster M, Sandor K, Müller J (1998) Entfernung von Schwermetallen aus einem Boden mit hohem Schluffanteil. Umweltwiss Schadst Forsch 10:99−106CrossRefGoogle Scholar
  25. Schwarzer M, Schuster M, von Hentig R (2000) Determination of palladium in gasoline by neutron activation analysis and automated column extraction. Fresenius J Anal Chem 368:240−243CrossRefGoogle Scholar
  26. Sievers H, Schuster M (2015) Trace analysis of platinum in raod dust samples by cloud point extraction and GFAAS. Analytical and Bioanalytical Chemistry in preparationGoogle Scholar
  27. Tilch J, Schuster M, Schwarzer M (2000) Determination of palladium in airborne particulate matter in a German city. Fresenius J Anal Chem 367:450−453CrossRefGoogle Scholar
  28. Unterreitmaier E, Schuster M (1995) Fluorometric detection of heavy metals with N-Methyl-N-9-(methylanthracene)-N’-benzoylthiourea. Anal Chim Acta 309:339CrossRefGoogle Scholar
  29. Vamnes JS, Lygre GB, Gronningsaeter AG, Gjerdet NR (2004) Four years of clinical experience with an adverse reaction unit for dental biomaterials. Commun Dent Oral Epidemiol 32:150−157CrossRefGoogle Scholar
  30. Vest P, Schuster M, König K-H (1989) Solventextraktion von Platinmetallen mit N-mono- und N, N-disubstituierten Benzoylthioharnstoffen. Fresenius Z Anal Chem 335:759CrossRefGoogle Scholar
  31. Vest P, Schuster M, König K-H (1991) Influence of tin(II) chloride on the solvent extraction of platinum group metals with N, N-di-n-hexyl-N’-benzoylthiourea. Fresenius J Anal Chem 339:142CrossRefGoogle Scholar
  32. Whiteley JD, Murry F (2005) Autocatalyst-derived platinum, palladium and rhodium (PGE) in infiltration basin and wetland sediments receiving urban runoff. Sci Total Environ 341:199−209CrossRefGoogle Scholar
  33. Zereini F, Zientek Ch, Urban H (1993) Konzentration und Verteilung von Platingruppenelementen (PGE) in Böden: Platinmetall-Emission durch Abrieb des Abgaskatalysatormaterials. Umweltwissenschaft und Schadstoff-Forschung 3:130−134CrossRefGoogle Scholar
  34. Zereini F, Skerstupp B, Urban H (1994) A Comparison between the use of sodium and lithium tetraborate in platinum-group elements determination by nickel sulphide fire-assay. Geostandards Newsletter 18:105−109CrossRefGoogle Scholar
  35. Zereini F, Wiseman C, Püttmann W (2007) Changes in palladium, platinum and rhodium concentrations and their spatial distribution in soils along a major highway in Germany from 1994 to 2004. Environ Sci Technol 41:451−456CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Fachgruppe Analytische ChemieTechnische Universität MünchenGarchingGermany

Personalised recommendations