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The quantity and quality of plant litter in the soil play an important role in the soil organic matter balance. Besides other pedo-climatic aspects, the content of recalcitrant molecules of plant residues and their chemical composition play a major role in the preservation of plant residues. In this study, we report that intrinsically resistant alkali-soluble bio-macromolecules extracted from maize plant (plant-humic acid) (plant-HA) contribute directly to the soil organic matter (OM) by its addition and conservation in the soil. Furthermore, we also observed that a high syringyl/guaiacyl (S/G) ratio in the lignin residues comprising the plant tissue, which modifies the microscopic structure of the alkali-soluble plant biopolymers, enhances their recalcitrance because of lower accessibility of molecules to degrading enzymes. These results are in agreement with a recent study, which showed that the humic substance of soil consists of a mixture of identifiable biopolymers obtained directly from plant tissues that are added annually by maize plant residues.

Pioneer plant species were observed growing on mined areas despite unfavourable conditions such as extreme pH, high salinity and phytotoxic levels of several elements. This study evaluated the contribution of pioneer species to the accumulation of soil organic matter (SOM). We collected 51 samples from 17 non-vegetated, natural and pioneer-vegetated sites in five highly saline mined areas in the Sierra de Cartagena (Spain). The composition of SOM was determined using total C, N and S elemental anlayzer, pyrolysis and solid state (13)C NMR spectroscopy. Results showed that pioneer species like Lygeum spartum had contributed approximately 11 kg SOM kg(-1) soil into the Balsa Rosa sites since 1991; it will take approximately 120 years of continuous growth for this plant to increase the SOM level comparable to natural site. In the Portman Bay area, Sarconia ramosissima and Phragmites australis can contribute SOM equivalent to present day SOM in natural sites in the next 30 years. Low quality SOM (C/N>20) deposited by pioneer plants was dominated by lignin-derived organic compounds such as phenols, guaiacols, syringols and aromatics while polyssacharides and alkyls were the major components in high quality SOM (C/N

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon ((OC)/l was investigated in a nine-step titration experiment (Cu/oC molar ratio = 0.0030-0.0567). We differentiated between soluble and insoluble Cu species by 0.45 mu m filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations ('free' Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (> 0.45 mu m) was the dominant Cu species for Cu/OC = 0.0030-0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 x 10(-6) - 5.58 x 10(-6) cm(2) s(-1)).

The interaction of Cu with dissolved organic matter (DOM, extracted from an organic forest floor) was investigated and the resulting data was evaluated in terms of their uncertainty. The speciation of Cu over free Cu (as analysed by diffusive gradients in thin films (DGT)), dissolved Cu–DOM complexes and precipitated Cu–DOM was determined as a function of pH (3.5, 4.0 and 4.5) and Cu/C ratio. The dissolved organically bound fraction was highest at pH 4.5, but this fraction decreased with increasing Cu/C ratio, which was observed for all pH levels. In the range of Cu=C ¼ 7 � 10 � 5 –2:3 � 10 � 2 (mol/mol) the precipitated fraction was very small. The speciation of both Al and Fe was not affected by increasing Cu concentrations. From a continuous distribution model using the Scatchard approach, we calculated the optimal fit and corresponding upper and lower 95% uncertainty bounds of the overall stability constants (Ko) with the shuffled complex evolution Metropolis (SCEM) algorithm. Although the optimal equation fitted the data very well, the uncertainty of the, according to literature, most reliable approach to establish stability constants, was still large. Accordingly, the usually reported intrinsic stability constants exhibited large uncertainty ranging from log Ki ¼ 6:0–7.1 (optimal 6.7) for pH 3.5, log Ki ¼ 6:5–7.1 (optimal 6.8) for pH 4.0, and log Ki ¼ 6:4–7.2 (optimal 6.8) for pH 4.5 and showed only little effect of pH. 2002 Elsevier Science Ltd. All rights reserved.

The composition of amorphous and condensed soil/sediment organic matter (SOM) domains was investigated for one soil sample and four sediment samples. These samples were oxidized with persulfate to remove amorphous SOM, before and after which the composition of SOM was studied by thermogravimetric analysis, pyrolysis-GC/MS, and cross polarization magic angle spinning 13C-NMR. Comparison of the SOM composition before and after oxidation showed that condensed SOM was more thermostable and less polar than amorphous SOM. Condensed SOM was relatively low in O–alkyl C and carboxyl C and it was likely to contain only small amounts of labile organic components (carbohydrates, peptides, fatty acids). Apart from these general characteristics, the composition of the condensed and amorphous domains appeared to be highly dependent on the origin and nature of the SOM investigated. Condensed domains in relatively undecomposed SOM were enriched in aliphatic C, whereas condensed domains in relatively weathered SOM were enriched in aromatic C. Altogether, the compositional changes upon persulfate oxidation were similar to the compositional changes upon humification, which supports the idea that weathered SOM is more condensed than the original material.