The influence of more than 100 years of fertilization with farmyard manure on soil organic matter in comparison to unfertilized soil was studied in particle-size fractions using elemental (C and N) analyses and pyrolysis-field ionization mass spectrometry. Distinct differences in C and N concentrations and distribution and in the quality of organic matter between the size fractions and the fertilization treatments were observed. Clay-associated C and N were relatively higher in the unfertilized treatment, whereas the application of farmyard manure preferentially increased soil organic matter associated with the fine and medium silt fractions. Pyrolysis-field ionization mass spectrometry of soil fractions < 20-mu-m showed increasing values for lignin monomers and dimers and fatty acids with larger equivalent diameters, whereas the proportion of N compounds, mono- and polysaccharides and phenolics decreased in the larger size fractions. Sand fractions were particularly rich in lignin fragments, mono- and polysaccharides, and alkanes/alkenes. These relationships seemed to be independent of management practices. In the same size fractions of the different treatments, however, a higher relative abundance of N-compounds, mono- and polysaccharides, phenolics, lignin monomers, and alkanes/alkenes was observed in the unfertilized variant. Lignin dimers and fatty acids were more abundant in the farmyard manure treatment. Both trends together imply that soil enrichment in organic matter due to the application of farmyard manure largely reflects an increase in lignin building blocks and partly reflects an increase in lipids such as fatty acids in the silt fractions. Therefore these constituents are of particular importance in assessing the positive effects of farmyard manure on soil fertility.