Copper complexation by dissolved organic matter and uncertainty assessment of their stability constants. Chemosphere 2002

Abstract 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 ÔfreeÕ 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 Â 10 À5 -2:3 Â 10 À2 (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 ¼ 6:0-7.1 (optimal 6.7) for pH 3.5, log K i ¼ 6:5-7.1 (optimal 6.8) for pH 4.0, and log K i ¼ 6:4-7.2 (optimal 6.8) for pH 4.5 and showed only little effect of pH

The applicability of accelerated solvent extraction (ASE) to extract lipid biomarkers from soils

We investigated the ability of accelerated solvent extraction (ASE) to extract selected lipid biomarkers (C19–C34 n-alkanes, n-alcohols and n-fatty acids as well as dehydroabietic acid and β-sitosterol) from a sandy soil profile under Corsican pine. Two organic layers (moss and F1) as well as two mineral soil horizons (EA and C1) were sampled and extracted with DCM/MeOH (93:7 v/v) by ASE at 75 °C and a pressure of 6.9 × 106 Pa or 17 × 106 Pa. Soxhlet extractions were used as the established reference method. After clean-up and derivatization with BSTFA, the extracts were analyzed on GC/MS. Using Soxhlet as a reference, we found ASE to extract all compounds adequately. The n-alkanes, especially, were found to be extracted very efficiently from all horizons studied. Only the n-fatty acids and β-sitosterol from the organic layers seemed to be extracted at a slightly lower efficiency by ASE. In all but two instances the relative abundance of extracted lipids within a component class was the same regardless of the extraction method used. Using a higher pressure in the ASE extractions significantly increased the extraction efficiency for all component classes in the moss layer, except β-sitosterol. The effect was most pronounced for the n-alkanes. In the EA horizon, a higher pressure slightly reduced the extraction efficiency for dehydroabietic acid. The observed differences between ASE and Soxhlet extractions as well as the pressure effect can be explained by a decrease in polarity of the extractant due to the elevated pressure and temperature applied during ASE extractions as compared to Soxhlet extractions. This would mainly increase the extraction efficiency of the least polar biomarkers: the n-alkanes as was observed. In addition, a better penetration of still partially water-filled micro pores under elevated pressure and temperature may have played a role

Radiocarbon Dating of Soil Organic Matter Fractions in Andosols in Northern Ecuador

Volcanic ash soils (Andosols) may offer great opportunities for paleoecological studies, as suggested by their characteristic accumulation of organic matter (OM). However, understanding of the chronostratigraphy of soil organic matter (SOM) is required. Therefore, radiocarbon dating of SOM is necessary, but unfortunately not straightforward. Dating of fractions of SOM obtained by alkali-acid extraction is promising, but which fraction (humic acid or humin) renders the most accurate 14C dates is still subject to debate. To determine which fraction should be used for 14C dating of Andosols and to evaluate if the chronostratigraphy of SOM is suitable for paleoecological research, we measured 14C ages of both fractions and related calibrated ages to soil depth for Andosols in northern Ecuador. We compared the time frames covered by the Andosols with those of peat sequences nearby to provide independent evidence. Humic acid (HA) was significantly older than humin, except for the mineral soil samples just beneath a forest floor (organic horizons), where the opposite was true. In peat sections, 14C ages of HA and humin were equally accurate. In the soils, calibrated ages increased significantly with increasing depth. Age inversions and homogenization were not observed at the applied sampling distances. We conclude that in Andosols lacking a thick organic horizon, dating of HA renders the most accurate results, since humin was contaminated by roots. On the other hand, in mineral soil samples just beneath a forest floor, humin ages were more accurate because HA was then contaminated by younger HA illuviated from the organic horizons. Overall, the chronostratigraphy of SOM in the studied Andosols appears to be suitable for paleoecological research

Radiocarbon Dating of Soil Organic Matter Fractions in Andosols in Northern Ecuador

Volcanic ash soils (Andosols) may offer great opportunities for paleoecological studies, as suggested by their characteristic accumulation of organic matter (OM). However, understanding of the chronostratigraphy of soil organic matter (SOM) is required. Therefore, radiocarbon dating of SOM is necessary, but unfortunately not straightforward. Dating of fractions of SOM obtained by alkali-acid extraction is promising, but which fraction (humic acid or humin) renders the most accurate 14C dates is still subject to debate. To determine which fraction should be used for 14C dating of Andosols and to evaluate if the chronostratigraphy of SOM is suitable for paleoecological research, we measured 14C ages of both fractions and related calibrated ages to soil depth for Andosols in northern Ecuador. We compared the time frames covered by the Andosols with those of peat sequences nearby to provide independent evidence. Humic acid (HA) was significantly older than humin, except for the mineral soil samples just beneath a forest floor (organic horizons), where the opposite was true. In peat sections, 14C ages of HA and humin were equally accurate. In the soils, calibrated ages increased significantly with increasing depth. Age inversions and homogenization were not observed at the applied sampling distances. We conclude that in Andosols lacking a thick organic horizon, dating of HA renders the most accurate results, since humin was contaminated by roots. On the other hand, in mineral soil samples just beneath a forest floor, humin ages were more accurate because HA was then contaminated by younger HA illuviated from the organic horizons. Overall, the chronostratigraphy of SOM in the studied Andosols appears to be suitable for paleoecological research.

Improved treatment of uncertainty in hydrologic modelling: combining the strengths of global optimisation and data assimilation

Hydrologic models use relatively simple mathematical equations to conceptualize and aggregate the complex, spatially distributed, and highly interrelated water, energy, and vegetation processes in a watershed. A consequence of process aggregation is that the model parameters often do not represent directly measurable entities and must therefore be estimated using measurements of the system inputs and outputs. During this process, known as model calibration, the parameters are adjusted so that the behavior of the model approximates, as closely and consistently as possible, the observed response of the hydrologic system over some historical period of time. In practice, however, because of errors in the model structure and the input (forcing) and output data, this has proven to be difficult, leading to considerable uncertainty in the model predictions. This paper surveys the limitations of current model calibration methodologies, which treat the uncertainty in the input-output relationship as being primarily attributable to uncertainty in the parameters and presents a simultaneous optimization and data assimilation (SODA) method, which improves the treatment of uncertainty in hydrologic modeling. The usefulness and applicability of SODA is demonstrated by means of a pilot study using data from the Leaf River watershed in Mississippi and a simple hydrologic model with typical conceptual components