Cycling of rare earth elements in the atmosphere in central Tokyo

Concentrations of 14 rare earth elements (REEs) in six size classes of airborne particulate matter (APM) (<0.43, 0.43-0.65, 0.65-1.1, 1.1-2.1, 2.1-11, and >11 μm) and in two different phases (suspended particulate and dissolved) in rainwater were determined by inductively coupled plasma mass spectrometry (ICP-MS). Positive Eu and Tb anomalies were observed in size-classified APM. These anomalies may be due to large emissions of Eu and Tb to the atmosphere resulting from the recent change in Japan from the use of cathode-ray tubes to plasma displays in television sets (Eu and Tb) and from the widespread use of magneto-optical disks (Tb). The light REEs were enriched in fine APM particles (diameter < 1.1 μm). Because compositions of La/Ce/Sm in fine APM (diameter < 1.1 μm) were similar to those in automobile catalyst, the light REE enrichment was attributed to automobile emissions. In contrast, the REE distribution pattern in the suspended particulate phase in rainwater was similar to that in coarse APM (diameter > 2.1 μm), and a positive Tb anomaly was observed, suggesting that coarse particles easily become trapped in rain droplets. A negative Eu anomaly was observed in the dissolved phase in rainwater, but not in APM or in the suspended particulate phase in rainwater. Unlike other REEs, Eu can exist as both bivalent and trivalent ions in nature, and Eu-selective dissolution from or adsorption onto the trapped particles of Eu might account for the negative anomaly. These results show that atmospheric REE cycling is affected by the physico-chemical properties of APM.