Fluorine-, boron- and magnesium-rich metamorphosed xenoliths occur in the Campanian Ignimbrite deposits at Fiano (southern Italy), at ∼50 km northeast of the sourced volcanic area. These rocks originated from Mesozoic limestones of the Campanian Apennines, embedded in a fluid flow. The Fiano xenoliths studied consist of ten fluorophlogopite-bearing calc-silicate rocks and five carbonate xenoliths, characterized by combining mineralogical analyses with whole-rock and stable isotope data. The micaceous xenoliths are composed of abundant idiomorphic fluorophlogopite, widespread fluorite, F-rich chondrodite, fluoborite, diopside, Fe(Mg)-oxides, calcite, humite, K-bearing fluoro-richterite and grossular. Of the five mica-free xenoliths, two are calcite marbles, containing subordinate fluorite and hematite, and three are weakly metamorphosed carbonates, composed only of calcite. The crystal structure and composition of fluorophlogopite approach that of the end-member. The Fiano xenoliths are enriched in trace elements with respect to the primary limestones. Comparisons between the rare-earth element (REE) patterns of the Fiano xenoliths and those of both Campanian Ignimbrite and Somma-Vesuvius marble and carbonate xenoliths showthat the Fiano pattern overlaps that of Somma-Vesuvius marble and carbonate xenoliths, and reproduces the trend of Campanian Ignimbrite rocks. Values of δ13C and δ18O depict the same trend of depletion in the heavy isotopes observed in the Somma-Vesuvius nodules, and is related to thermometamorphism. Trace-element distribution, paragenesis, stable isotope geochemistry and data modelling point to infiltration of steam enriched in F, B,Mg and As into carbonate rocks at a temperature of ∼300–450°C during the emplacement of the Campanian Ignimbrite.

Clearly defined distal tephras are rare in rockshelter sediment records. Crvena Stijena, a Palaeolithic site in Montenegro, contains one of the longest (> 20 m) rockshelter sediment records in Europe with deposits ranging in age from Middle Pleistocene to mid-Holocene. A distinctive tephra is clearly exposed within the well stratified record approximately 6.5 m below the present land surface. We present geochemical data to confirm that this tephra is a distal equivalent of the Campanian Ignimbrite deposits and a product of the largest Late Pleistocene eruption in Europe. Originating in the Campanian volcanic province of southwest Italy, this tephra has been independently dated to 39.3 ka. It is a highly significant chronostratigraphic marker for southern Europe. Macrostratigraphic and microstratigraphic observations, allied with detailed particle size data, show that the tephra layer is in a primary depositional context and was transported into the rockshelter by aeolian processes. This site is unique because the tephra forms an abrupt boundary between the Middle and Upper Palaeolithic records. Before they can be used as chronostratigraphic markers in rockshelter and cave-mouth environments, it is essential to establish the stratigraphic integrity of distal tephras and the mechanisms and pathways involved in their transport and deposition.

The presence of an independently dated marker in an archaeological site offers rare opportunities for assessing the reliability of radiocarbon dates, especially when these are close to the age limit of the technique. Two different pretreatment protocols (routine ABA and more rigorous ABOx-SC) were employed in the chemical preparation of the same charcoal sample from a layer closely associated to the Campanian Ignimbrite tephra at the Russian Palaeolithic site of Kostenki 14 (Markina Gora). The ABA-treated fraction gave an age of ∽33 14C ka BP, comparable to a previous determination from the same layer, whereas the ABOx-SC produced an older age of ∽35 14C ka BP. This is the first radiocarbon determination of an archaeological sample to provide an age consistent with the "calendar" age for the CI tephra marker.