Sulfur fixation in wood mapped by synchrotron X-ray studies: implications for environmental archives

There is a shortage of archives of sulfur that can be used to investigate industrial orvolcanic pollution in terrestrial catchments, but the role of S as a nutrient, coupled with sparse published evidence, suggests that trees are promising targets. We focused on two conifer species (Picea abies (L.) Karst and Abies alba Miller) from an Alpine site in NE Italy. Bulk analyses of Abies demonstrate that S concentrations were higher in the second half of the 20th century but with some high outliers possibly reflecting particulate impurities. X-ray synchrotron analyses confirmed the observed time trend, which is similar to that of a nearby stalagmite, and reflects an atmospheric pollution record mediated by storage in the soil and ecosystem. S and P were found to be localized in the inner cell wall (ca. 2 microm wide), local thickenings of which probably account for some outlying high values of S in synchrotron studies. S occurs as a mixture of oxidation states (0 to +0.5, +2, +5, and +6) which are consistent in space and time. The results indicate that wood older than a few years contains archive-quality S but that robust conclusions require multiple replicate analyses.