The Chemical Forms and Plant Availability of Copper in Composting Organic Wastes
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AbstractA seven-step sequential extraction scheme was used to track changes in operationally defined copper speciation during the composting of a mixture of grass clippings and sawdust originating from tanalised timber. Starting materials were either unamended or treated with differing amounts of soluble copper, using a copper acetate solution, and then composted in the laboratory. Results showed that at the start of the experiment over 80% of the copper present in the unamended materials occurred in forms not immediately available for plant uptake. However, composting processes enabled the release of this copper which then, over time, became more bioavailable. Large amounts of copper in the copper amended materials were initially detectable in all fractions except the residual one, but over time it was seen to move from all fractions to the EDTA extractable fraction, thought to determine organically complexed / chelatable metals (Amir, 2005). This continued until an equilibrium was reached and then the water and calcium nitrate extractable forms appeared to hold the excess. Copper as determined by these extracts would be available for plant uptake. In the second experiment, three different organic wastes (grass/sawdust, pig slurry/sawdust and sewage sludge cake/sawdust) to which copper had been added as copper acetate, sulphate or EDTA, were composted in the laboratory. Samples were taken at 0, 105 and 318 days and subjected to a range of analyses: copper by sequential extraction using two different extraction schemes, a chelating resin membrane (CRM) procedure and by XRF spectrometry; FTIR analysis for functional groups; total carbon, nitrogen and sulphur; pH, EC, NH4+ and NO3- nitrogen, COD, germination indices and optical properties of water extracts. Sequential extractions demonstrated clear changes in copper distribution amongst various fractions within the materials, with copper originally present in the materials being transferred from the oxidisable fractions to easily extractable (and hence potentially phytoavailable) fractions. Transfer of copper from available to less available fractions in copper amended materials was also seen with movement of copper within copper EDTA treated materials being the slowest of all. Initial amounts of copper in fraction 1 extracted from all samples determined the rate at which copper was transformed. CRM determined copper correlated strongly with copper from fraction 1 of the Tessier scheme, although changes over time did not correspond well. Other parameters measured indicated that that the material was maturing (decreases in C/N and polysaccharide functional groups). However, other results demonstrated that the composts were still immature and unstable. Such slow decomposition was attributed to the high lignin content of the materials. Nevertheless, immobilisation of potentially phytotoxic level of copper was still demonstrated. The usefulness of chelating resin membrane as a predictor of phytoavailable copper is also discussed.
PublisherUniversity of Wolverhampton
DescriptionSubmitted in partial fulfilment of the requirements of the University of Wolverhampton for the Degree of Doctor of Philosophy