Sulfur dynamics during long-term ecosystem development

Long-term soil and ecosystem development involves predictable changes in nitrogen (N) and phosphorus (P) availability and limitation, but far less is known about comparable changes in sulfur (S) despite its importance as an essential plant macronutrient and component of soil organic matter. We used a combination of elemental analysis, X-ray absorption spectroscopy, hydrolytic enzyme assays, and stable S isotope ratios to examine S in soil and leaf tissue along the 120,000-year Franz Josef chronosequence, New Zealand. Total soil S concentrations increased during the early stages of pedogenesis and then declined as soils aged. There was little variation in soil N:S ratios along the chronosequence other than in the youngest (5 year old) soil, although the carbon (C):S ratio increased markedly in the oldest soils and the P:S ratio decreased continuously along the chronosequence. Foliar S concentrations and N:S ratios varied widely among common plant species but did not change consistently with increasing soil age, although foliar P:S declined for several species in the older stages of the chronosequence. The chemical nature of soil organic S extracted from mineral and organic horizons and determined by S K-edge X-ray absorption near-edge fine-structure (XANES) spectroscopy was dominated by C-bonded S distributed approximately equally in highly-reduced and intermediate oxidation states, although ester-bonded S was also abundant throughout the chronosequence. Soil sulfatase activity expressed on a soil C basis was highest in young soils, indicating low S availability in the early stage of pedogenesis. Enzymatic C:S and N:S ratios varied little during ecosystem development, although the enzymatic P:S ratio increased continuously along the chronosequence. Stable S isotope ratios (δ34S) increased along the chronosequence, particularly in the early stages of pedogenesis, reflecting a shift in S inputs from primary mineral S to oceanic sulfate in atmospheric deposition. Overall, this first comprehensive assessment of S along a long-term soil chronosequence suggests that S availability is low in the earliest stage of pedogenesis, but then remains stable throughout the progressive and retrogressive phases of ecosystem development, despite pronounced shifts in the chemistry and dynamics of other nutrients.