The ligands complexing copper in various organic matter fractions isol
ated from a soil treated with copper-contaminated sewage sludge have b
een characterized using electron paramagnetic resonance (EPR) spectros
copy. A soil of the Countesswells series was treated with sewage sludg
e at the rate of 100 t dry matter/ha. Copper in the form of copper car
bonate was then applied to give copper loadings of 140 mg/kg and 280 m
g/kg in the top 25 cm of the profile, values at the EEC directive limi
ting values and at twice these values, respectively. After 3 years, th
e soil was sampled to a depth of 10 cm for analysis. Soil solution obt
ained by centrifugation of fresh soil contained organically-complexed
copper. The EPR spectroscopic parameters (A11 and g11) for Cu have val
ues consistent with the presence of oxygen coordination at the equator
ial position. Organic matter was isolated from soil by successive extr
actions with 0.1 M sodium pyrophosphate (pH 7) and 0.1 M sodium hydrox
ide and fractionated by selective adsorption and precipitation procedu
res. Copper was present in several different complexes. Hyperfine stru
cture from N-14 was observed in pyrophosphate extract unprecipitated b
y 80% ethanol, the fulvic acid and humic acid fractions, indicating th
at copper was in coordination with at least two nitrogen atoms in thes
e fractions. The precipitable pyrophosphate-extracted substances only
contained oxygen ligands. Soil solutions from three other soil series
from sites which had received contaminated sludge treatments 20 years
previously were also examined. Their spectra at 100 K were dominated b
y manganese(II) signals but a copper signal could be resolved which wa
s indistinguishable from that from the Countesswells series soil.