Trace element distribution in annual stalagmite laminae mapped by micrometer-resolution X-ray fluorescence: Implications for incorporation of environmentally significant species

Stalagmite ER78, from Grotta di Ernesto cave in NE Italy displays clear annual lamination consistent with its shallow depth below a forest ecosystem subject to autumnal peaking of water infiltration. Synchrotron radiation scanning micro-X-ray fluorescence analyses of heavy elements at European Synchrotron Radiation Facility beamline ID22, and light elements at ID21, with 1–3 μm resolution has been combined with data from ion microprobe analyses to reveal chemical variability across the visible layers of these annual laminae. A series of elements display a symmetrical peak, centered around the thin, dark layer at the top of each lamina. The peak concentration is ordered Y > Zn, Cu and Pb > P and Br. This hierarchy is thought to reflect the selectivity of transport of these elements, possibly by organic colloids flushed from the soil zone during autumn infiltration. Ion microprobe analysis indicates Na and F also increase, as does H, the latter reflecting increased microporosity. Sr displays a trough around the dark and thin autumn layer implying that its incorporation may be limited by competition with other elements. Mg and S show a different pattern of annual variation and Fe displays none. The trace metals, Br and Y display peak abundance in the early 20th century, which appears to reflect a period of tree-felling rather than a climatic anomaly. The results demonstrate the power of the high spatial resolution and low detection limits of the synchrotron technique, and its ability to produce quantitative maps that allow distinction of layered structure from that of isolated particles, or irregular inhomogeneities.