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Uptake of the trace metals, Pd, Cd, Hg and Pb, by the marine macroalga, Ulva lactuca, has been studied along a salinity gradient (S = 15–35; pH ~ 8.3) created by batch mixing of synthetic sea water and pure water, both in the absence and presence of humic substances. Factors defining the concentration ratio of metal taken up (w/w) to metal remaining in solution ranged from about 102 mL g− 1 for Cd to 103 mL g− 1 for Pd and Hg. Within experimental error, only the biouptake of Cd appeared to exhibit a dependence on salinity, while the addition of 3 mg L− 1 of humics resulted in a small suppression of Pd and Hg uptake and a moderate enhancement of Pb uptake compared with the humic-free system. Metal internalisation, evaluated from an EDTA wash of the alga, followed the sequence: Hg > Pd > Cd > Pb; and was notably inhibited in the presence of humics for Pb. Metal uptake (as adsorption and internalisation) was modelled using the Windermere Humic Aqueous Model (WHAM, v6) by encoding the macroalga as a polyelectrolytic binding phase whose properties were defaulted to those of aqueous humics in the software database. By setting the “activity” of the binding phase to about 0.1 and systematically reducing the default constants for metal binding, the magnitude of metal uptake by U. lactuca was reproduced. However, for all metals the model predicted a reduction in algal uptake as a function of salinity that was not always observed experimentally. Moreover, calculations performed in the presence of aqueous humic substances and using the earlier fitted constants significantly underestimated metal uptake by U. lactuca. Discrepancies between experimental observations and model calculations, which are attributed to the formation of ternary complexes at the algal surface, suggest that conventional equilibrium speciation considerations alone are not applicable for modelling metal interactions with marine macroalgae.  相似文献   
2.
Attributing the start of peat growth to an absolute timescale requires dating the bottom of peat deposits overlying mineral sediment, often called the basal peat. Peat initiation is reflected in the stratigraphy as a gradual transition from mineral sediment to increasingly organic material, up to where it is called peat. So far, varying criteria have been used to define basal peat, resulting in divergent approaches to date peat initiation. The lack of a universally applicable and quantitative definition, combined with multiple concerns that have been raised previously regarding the radiocarbon dating of peat, may result in apparent ages that are either too old or too young for the timing of peat initiation. Here, we aim to formulate updated recommendations for dating peat initiation. We provide a conceptual framework that supports the use of the organic matter (OM) gradient for a quantitative and reproducible definition of the mineral-to-peat transition (i.e., the stratigraphical range reflecting the timespan of the peat initiation process) and the layer defined as basal peat (i.e., the stratigraphical layer that is defined as the bottom of a peat deposit). Selection of dating samples is often challenging due to poor preservation of plant macrofossils in basal peat, and the representativity of humic and humin dates for the age of basal peat is uncertain. We therefore analyse the mineral-to-peat transition based on three highly detailed sequences of radiocarbon dates, including dates of plant macrofossils and the humic and humin fractions obtained from bulk samples. Our case study peatland in the Netherlands currently harbours a bog vegetation, but biostratigraphical analyses show that during peat initiation the vegetation was mesotrophic. Results show that plant macrofossils provide the most accurate age in the mineral-to-peat transition and are therefore recommendable to use for 14C dating basal peat. If these are unattainable, the humic fraction provides the best alternative and is interpreted as a terminus-ante-quem for peat initiation. The potential large age difference between dates of plant macrofossils and humic or humin dates (up to ∼1700 years between macrofossil and humic ages, and with even larger differences for humins) suggests that studies reusing existing bulk dates of basal peat should take great care in data interpretation. The potentially long timespan of the peat initiation process (with medians of ∼1000, ∼1300 and ∼1500 years within our case study peatland) demonstrates that choices regarding sampling size and resolution need to be well substantiated. We summarise our findings as a set of recommendations for dating basal peats, and advocate the widespread use of OM determination to obtain a low-cost, quantitative and reproducible definition of basal peat that eases intercomparison of studies.  相似文献   
3.
As part of a study on microbial redox alteration of humic substances we investigated the potential effect of this metabolism on the fate of heavy metals and hydrocarbons as a result of conformational alteration of the humic molecular structure due to microbial reduction. Our studies indicate that the microbial reduction of humic acids (HA) results in significant morphological and geochemical alterations. X‐ray microscopy analysis indicate that the conformational structure of the humic colloids is altered as a result of the redox change. In the reduced state, the HA appeared as small dense particles, on reoxidation, large loose aggregates were formed. In addition, spectrofluorometric studies indicated that the binding capacity of the HA for naphthalene was decreased by 10% when the HA was reduced. Similarly, the reduced HA yielded higher surface tension values at all concentrations tested which is indicative of a more hydrophilic and less hydrophobic solute. On reoxidation, the surface tension values reverted back to values similar to those obtained for the untreated oxidized HA. These data indicate that the hydrophobicity of the HA is altered on biological reduction of the HA and that this alteration is reversible. In contrast the reduced HA demonstrated a 15% higher affinity for heavy metals such as divalent cobalt than the oxidized HA. In addition to increasing the binding capacity of HA for heavy metals, the reduction of the HA also decreased the bioavailability and toxicity of bound heavy metals such as chromium. When incubated in the presence of Cr(III) and HA, cells of Escherichia coli grew much more rapidly in the presence of the reduced HA suggesting that the higher metal binding capacity of the reduced humic substances resulted in a removal of the Cr(III) from solution and hence reduced its bioavailability and toxicity. These studies demonstrate that HA redox state and reduction of humic acids by microorganisms can have a significant effect on the molecular morphology and binding constants of HA for heavy metals and hydrocarbons and also directly affects the bioavailability of these compounds in the environment.  相似文献   
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