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Abstract Peat accumulation makes nutrient-limited ombrotrophic bogs important carbon sinks, while enhanced atmospheric nitrogen (N) deposition threatens this capacity. Here we show that the stoichiometry of peat and porewater, a control of plant growth and decomposition, has been altered in response to long-term N, phosphorus (P), and potassium (K) fertilization at Mer Bleue ombrotrophic bog in eastern Ontario, Canada. In N-fertilized peat, receiving up to an additional 6.4 g N m−2 y−1 above ambient deposition, we found N significantly (p < 0.05) greater, P both significantly greater and smaller dependent on treatment concentration, calcium (Ca) and K concentrations significantly lower, relative to control plots. In NPK-fertilized peat, P was greater than control while Ca was significantly smaller. In the porewater of N- and NPK-fertilized peat, we observed significantly more ammonium, nitrate, dissolved organic nitrogen, phosphate, and dissolved organic phosphorus than in the controls. Fourier-transform infrared (FTIR) spectroscopic analysis demonstrated that fertilization in all treatments increased decomposition, as indicated by residual enrichment of refractory moieties such as aromatics, carboxylates, and lignin, albeit only in the uppermost depths. Changes in peat quality may, however, not only relate to advanced decomposition but also to changes in litter input, as predominant vascular vegetation in the fertilized plots shared several features in FTIR spectra with samples of uppermost peat layers. Our results demonstrate that the peat in this ombrotrophic bog has responded to long-term fertilization with loss of Sphagnum moss and its filter function, increased shrub cover and enhanced decomposition. Highlights • Nutrient addition resulted in changes from moss to shrub dominance and a lowered peat surface. • There were significant increases in peat N and P and decreases in Ca and K concentrations. • Peat porewater had significant increases in N and P, with greatest changes in top 20 cm. • FTIR spectra of surface peat indicated advanced decomposition and altered vegetation. • These changes result from both direct nutrient additions and secondary vegetation changes. [ABSTRACT FROM AUTHOR]