Modelling the equilibrium speciation of nickel in the Tweed Estuary, UK: Voltammetric determinations and simulations using WHAM

The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 10¹⁹ and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries.     

Glacio-lacustrine stratigraphy,aquifer characterization and contaminant transport: a case study in South Lake Tahoe,California, USA

A hydrogeologic model that has been used by many researchers and consultants to describe an area of South Lake Tahoe, California, USA impacted by MTBE contamination describes a relatively homogeneous unconfined aquifer comprised of poorly sorted glacial outwash deposits, within which water-supply wells are able to exert significant alteration in natural groundwater flow. A re-examination of the area’s hydrogeology is presented, which supports a layered heterogeneous aquifer system constructed of alternating fine and coarser-grained glacio-lacustrine depositional units. This re-evaluation was accomplished through a review of lithologic logs across an area of approximately 1 km², combined with observations of significant hydraulic head differences and knowledge of the depositional environments controlled by Pleistocene Lake Tahoe high stands. Many of the fine-grained units observed at depths from 6 to 15 m, although relatively thin, are generally continuous and serve as significant barriers to groundwater flow. The vertical migration of contamination across these fine-grained units to deeper groundwaters was facilitated by cross-screened monitoring wells installed as part of site investigation activities. This conclusion highlights the importance of geologic characterization and proper monitoring well construction at contaminated site investigations.

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Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

Nucleosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites

Stepwise dissolutions of the carbonaceous chondrites Orgueil (CI), Murchison (CM) and Allende (CV) reveal large nucleosynthetic anomalies for Zr isotopes that contrast with the uniform compositions found in bulk meteorites. Two complementary nucleosynthetic components are observed: one enriched and one depleted in s-process nuclides. The latter component, characterized by excess ⁹⁶Zr, is most distinctive in the acetic acid leachate (up to ε⁹⁶Zr ≈ 50). The excess decreases with increasing acid strength and the final leaching steps of the experiment are depleted in ⁹⁶Zr and thus enriched in s-process nuclides. Presolar silicon carbide grains are likely host phases for part of the anomalous Zr released during these later stages. However, by mass balance they cannot account for the ⁹⁶Zr excesses observed in the early leaching steps and this therefore hints at the presence of at least one additional carrier phase with significant amounts of anomalous Zr. The data provide evidence that average solar system material consists of a homogenized mixture of different nucleosynthetic components, which can be partly resolved by leaching experiments of carbonaceous chondrites.     

Long-term deforestation in NW Spain: linking the Holocene fire history to vegetation change and human activities

The Holocene fire regime is thought to have had a key role in deforestation and shrubland expansion in Galicia (NW Spain) but the contribution of past societies to vegetation burning remains poorly understood. This may be, in part, due to the fact that detailed fire records from areas in close proximity to archaeological sites are scarce. To fill this gap, we performed charcoal analysis in five colluvial soils from an archaeological area (Campo Lameiro) and compared the results to earlier studies from this area and palaeo-ecological literature from NW Spain. This analysis allowed for the reconstruction of the vegetation and fire dynamics in the area during the last ca 11 000 yrs. In the Early Holocene, Fabaceae and Betula sp. were dominant in the charcoal record. Quercus sp. started to replace these species around 10 000 cal BP, forming a deciduous forest that prevailed during the Holocene Thermal Maximum until ～5500 cal BP. Following that, several cycles of potentially fire-induced forest regression with subsequent incomplete recovery eventually led to the formation of an open landscape dominated by shrubs (Erica sp. and Fabaceae). Major episodes of forest regression were (1) ～5500–5000 cal BP, which marks the mid-Holocene cooling after the Holocene Thermal Maximum, but also the period during which agropastoral activities in NW Spain became widespread, and (2) ～2000–1500 cal BP, which corresponds roughly to the end of the Roman Warm Period and the transition from the Roman to the Germanic period. The low degree of chronological precision, which is inherent in fire history reconstructions from colluvial soils, made it impossible to distinguish climatic from human-induced fires. Nonetheless, the abundance of synanthropic pollen indicators (e.g. Plantago lanceolata and Urtica dioica) since at least ～6000 cal BP strongly suggests that humans used fire to generate and maintain pasture.