RESUMEN

The Rio Santiago in the Cordillera Negra of Peru is severely contaminated by acid mine drainage in its headwaters. In a strongly acid stream, at about 3800 m above sea level (masl), microterraces were found with terrace walls built up of dead moss, with encrustations and interstitial fine, creamy sediment. The stream water was turbid due to the presence of similar suspended sediment, which also occurred as a thin basal layer in inter-rim basins. The moss was identified as the rare bryophyte Anomobryum prostratum (Müll. Hal.) Besch. Chemical and mineralogical analyses show that green, living parts of the moss are gradually coated by Al/Fe (hydr)oxides, inducing their senescence and death. The necromass is covered by creamy crusts through precipitation of schwertmannite-type material from the stream water and simultaneous 'capture' of fine sediment. The latter consists of a mixture of precipitate and fine detrital primary minerals. These processes are held responsible for the formation of the microterraces, which regarding their composition and environment seem to be unique. Remarkable is the high As content of the creamy crusts and sediment, attributed to strong sorption of As, whereas its solute concentration is relatively low. This calls for more attention to suspended fine sediment in the assessment of environmental risks of stream water use. Lastly, the results raise serious doubts about the use of aquatic bryophytes as bioindicator for chemical pollution in acid mine drainage-polluted streams.

RESUMEN

Tannins are ubiquitous in higher plants and also in litter and soils where they affect many biogeochemical processes. Despite this well-recognized role, their fate in litter and mineral soils is hardly known, as often only trace amounts, if any, are measured. In this study, we conducted an incubation experiment with Corsican pine litter to which known amounts of tannic acid (TA) or condensed tannins (CTs) from Corsican pine were added. Using Folin-Ciocalteu as a measure for total phenolics and HCl-butanol as an assay specific for CTs, acetone/water extractable phenolics and tannins decreased with time towards very low levels. Application of thermally assisted hydrolysis and methylation to litter before and after acetone/water extraction revealed that TA concentration decreased. By contrast, CTs remained to a great extent in the litter and could not be extracted suggesting that they were tightly bound.

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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 microm 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 microm) 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)).

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RESUMEN

Each plant species has a unique chemical composition, and also within a given plant the various tissues differ from one another in their chemistry. These different compositions can be traced back after decay of the plant parts when they are transformed into soil organic matter (SOM). As a result, the composition of SOM reflects not only the plant origin, but also the various tissues, and the composition consequently provides an estimate of the contribution of above-ground vs. below-ground litter. From the latter distribution the extent of bioturbation (mixing of above-ground litter with the mineral soil) can be assessed. Application of thermally assisted hydrolysis and methylation (THM) using tetramethylammonium hydroxide (TMAH) and subsequent analysis by gas chromatography/mass spectrometry (GC/MS) releases all typical cutin- and suberin-derived aliphatic monomers (mono-, di- and trihydroxyalkanoic acids, alpha,omega-alkanedioic acids) as their methyl esters and/or ethers in a rapid manner. Using the distribution of omega-hydroxyalkanoic acids that are present in pine needle cutin (C(12) and C(14)) and not in root suberin, and those that are present in roots but not in needles (C(20) and C(22)), the extent of bioturbation (mixing of above-ground plant litter with the mineral soil) can be assessed. Similarly, the (9,16-dihydroxyhexadecanoic acid+9,10,18-trihydroxyoctadecanoic acid)/(C(20) + C(22) alpha,omega-alkanedioic acids) ratio reflects the degree of bioturbation. Three mineral soil profiles under Corsican pine with an A horizon that exhibited extensive bioturbation phenomena, and underlying C horizons with hardly any or no bioturbation, were investigated in order to examine the applicability of such an approach. It appeared that the A horizons contained all four mentioned omega-hydroxyalkanoic acids, while the C horizons contained virtually only the C(20) and C(22) members. The results not only suggest that bioturbation occurs in the A horizons, but also that possible illuviation or other transport mechanisms of omega-hydroxyalkanoic acids seem hardly ever or never to occur, which is a prerequisite for applying this biomarker approach in assessing degrees of bioturbation.

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One of the best approaches to date to obtain overall binding constants (Ko) for Al and dissolved organic matter (DOM) from acidic soil solutions is to collect 'free' Al data with diffusive gradients in thin films (DGT) and to infer the Ko values by fitting a continuous distribution model based on Scatchard plots. Although there is clear established literature demonstrating the usefulness of the Scatchard approach, relatively little attention has been given to a realistic assessment of the uncertainties associated with the final fitted Ko values. In this study we present an uncertainty analysis of the fitted Ko values using a synthetic dataset with different levels of random noise and a real data set using DGT data from an acidic soil solution. The parameters in the continuous distribution model and their corresponding upper and lower 95% uncertainty bounds were determined using the Shuffled Complex Evolution Metropolis (SCEM) algorithm. Although reasonable fits of the distribution model to the experimental data were obtained in all cases, an appreciable uncertainty in the resulting Ko values was found due to three main reasons. Firstly, obtaining 'free' Al data even with the DGT method is relatively difficult, leading to uncertainty in the data. Secondly, before Scatchard plots can be constructed, the maximum binding capacity (MBC) must be estimated. Any uncertainty in this MBC propagates into uncertainty associated with the final plots. Thirdly, as the final fitted Ko values are largely based on extrapolation, a small uncertainty in the fit of the binding data results in an appreciable uncertainty in the obtained Ko. Therefore, while trends in Ko for Al and DOM could easily be discerned and compared, the uncertainty in the Ko values hinders the application in quantitative speciation calculation. More comprehensive speciation models that avoid the use of Ko seem to fit better for this purpose.

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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 = 7 x 10(-5) -2.3 x 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 (K(o)) 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 K(i) = 6.0-7.1 (optimal 6.7) for pH 3.5, log K(i) = 6.5-7.1 (optimal 6.8) for pH 4.0, and log K(i) = 6.4-7.2 (optimal 6.8) for pH 4.5 and showed only little effect of pH.

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RESUMEN

To better understand the precipitation behaviour of dissolved organic matter induced by interactions with metals, a systematic titration experiment was conducted mimicking the soil solution conditions in an acidic, sandy soil. The variables of interest included the type of metal species (Al, Fe), the redox state [Fe(II), Fe(III)], the pH (3.5, 4.0, 4.5), the metal to organic carbon (M/C) ratio and the competition between Al and Fe. Precipitation of DOM-Al appeared to be strongly correlated with M/C ratio and the pH. For Fe(II) only little precipitation occurred, while the strongest flocculation degree was found after addition of Fe(III). In contrast to Al, hardly any correlation between DOM-Fe precipitation and pH was observed. Both reduction and oxidation of Fe was found and exhibited a strong effect on the precipitated amounts of DOM and Fe. In competition, Al determined the precipitation behaviour at lower M/C ratios (<0.10), while at higher M/C ratios Fe determined the flocculation. Below a M/C ratio of 0.06 Al was the dominant metal in the precipitates, especially at lower pH levels, while the opposite trend was found at M/C ratios above 0.06. Overall, Fe(III) gave the strongest flocculation, although Al influenced the impact of Fe(III) interactions with DOM in relation to pH and M/C ratio.