Direct speciation analysis of thallium based on solid phase extraction and specific retention of a Tl(III) complex on alumina coated with sodium dodecyl sulfate.

Alumina (Al2O3) with an average particle size of 63 µm was modified with the anionic surfactant sodium dodecyl sulfate (SDS) and then applied to (i) solid phase extraction and separation of both thallium(I) and thallium(III), and (ii) preconcentration of Tl(III) from waste water samples. Only Tl(III), in the form of its complex with diethylenetriaminepentaacetate (DTPA), was retained on the sorbent, from where it can be eluted with 40 % nitric acid. Thallium species were then quantified by ICP MS. The method was characterized by a LOD of 25 pg of Tl(I) and 160 pg of Tl(III) in 10 mL samples. A large excesses of Tl(I) over Tl(III) was tolerated, and relatively high levels of other metal ions, such as a 500-fold excess of Pb(II) and Cd(II), and a 2000-fold excess of Zn(II), respectively, do not interfere. The sorbent was easily prepared and possesses a high loading capacity, and these properties make it an attractive material for rapid and efficient extraction and speciation of Tl. Graphical abstract:Schematic of the SPE procedure for separation (with preconcentration) of Tl(III) from Tl(I) was developed and applied to direct speciation analysis of thallium in wastewater. Self-made columns packed with alumina coated with SDS were used. The method is resistant to interferences from Pb, Cd, Zn and tolerates a large excess of Tl(I) over Tl(III).

Mobility of toxic elements in carbonate sediments from a mining area in Poland.

The Boleslaw-Bukowno mining area in Poland is highly polluted by elements such as Zn, Pb, Cd and As. The reactivity and mobility of toxic elements such as Tl are poorly known. Here, we studied by sequential extraction the mobility of As, Cd, Co, Cr, Cu, Mn, Mo, Pb, Tl and Zn in sediments from two water reservoirs near Bukowno. Results show that available As, Co, Mn, Pb and Zn are found in carbonate minerals. Available Cd, Cu and Tl are found in sulphides and organic matter. The extractability of As, Cr, Mo and Tl was rather poor. By contrast, 85 % of total Cd, Pb and Zn was mobile. We discuss Tl and Mo association in carbonate sediments from ore deposits.

Basin-scale contributions of Cr, Ni and Co from Ortegal Complex to the surrounding coastal environment (SW Europe).

The enrichment of Cr and Ni in the coastal zones is usually associated with anthropogenic sources such as the tanning, galvanization, ceramic, and cement industries. However, geological complexes of specific lithologic composition located near shorelines may act as natural sources of metals to the continental shelf. Cape Ortegal (SW Europe) is an ultramafic complex that has Cr, Ni and Co enriched in rocks due to the minerals chromite, chromospinel, gersdorfite and pentlandite. Thus, the hypothesis that this geological complex contributes to metal enrichment in Ortigueira and Barqueiro Rias and the adjacent continental shelf was tested. Chromium, Ni, and Co were determined in water and in suspended particulate matter of ria tributaries, rainfall, surface sediments, mussels, and algae. High contents of Cr (max. 1670mg·kg(-1)) and Ni (max. 1360 mg · kg(-1)) were found in the sediments surrounding Cape Ortegal and the Ortigueira Ria as a result of erosion of exposed cliffs. Dissolved Cr and Ni concentrations in fluvial waters were significantly higher in the rivers that crosses the Ortegal Complex, i.e. Lourido (0.47 µg Cr · L(-1); 9.4 µg Ni · L(-1)) and Landoi (0.37 µg Cr · L(-1); 4.3 µg Ni · L(-1)), in comparison with the nearby basin out of the complex influence (Sor River: <0.01 µg Cr · L(-1); 0.57 µg Ni · L(-1)). The annual fluvial contributions of Cr and Ni to the Ortigueira Ria were higher than fluxes into the Barqueiro Ria. Moreover, the increase in Cr and Ni in the rainfall in summer demonstrated the importance of the atmosphere pathway for introducing these elements into the aquatic environment. As a consequence, the contents of these metals in soft tissues and shell of mussels and algae from the Ortigueira Ria were higher than the organisms from Barqueiro Ria. Thus, geological complexes, such as the Cape Ortegal, located in an uncontaminated area, can increase the land-sea exchange of trace metals.

Temperature-dependent sex determination in fish revisited: prevalence, a single sex ratio response pattern, and possible effects of climate change.

BACKGROUND: In gonochoristic vertebrates, sex determination mechanisms can be classified as genotypic (GSD) or temperature-dependent (TSD). Some cases of TSD in fish have been questioned, but the prevalent view is that TSD is very common in this group of animals, with three different response patterns to temperature. METHODOLOGY/PRINCIPAL FINDINGS: We analyzed field and laboratory data for the 59 fish species where TSD has been explicitly or implicitly claimed so far. For each species, we compiled data on the presence or absence of sex chromosomes and determined if the sex ratio response was obtained within temperatures that the species experiences in the wild. If so, we studied whether this response was statistically significant. We found evidence that many cases of observed sex ratio shifts in response to temperature reveal thermal alterations of an otherwise predominately GSD mechanism rather than the presence of TSD. We also show that in those fish species that actually have TSD, sex ratio response to increasing temperatures invariably results in highly male-biased sex ratios, and that even small changes of just 1-2 degrees C can significantly alter the sex ratio from 1:1 (males:females) up to 3:1 in both freshwater and marine species. CONCLUSIONS/SIGNIFICANCE: We demonstrate that TSD in fish is far less widespread than currently believed, suggesting that TSD is clearly the exception in fish sex determination. Further, species with TSD exhibit only one general sex ratio response pattern to temperature. However, the viability of some fish populations with TSD can be compromised through alterations in their sex ratios as a response to temperature fluctuations of the magnitude predicted by climate change.