Hazard potential of widespread but hidden historic offshore heavy metal (Pb, Zn) contamination (Gulf of Cadiz, Spain).

Natural and human-induced seabed sediment disturbances affect wide areas of the global coastal ocean. These recurrent to chronic disturbances mobilize significant amounts of material, including substances that have the potential to significantly harm the environment once re-released. This very challenging issue is difficult to deal with if sub-surface contaminant concentrations are unknown. Based on the analysis of 11 new, up to 5-m long sediment cores taken offshore in the Gulf of Cadiz, the contamination history (using the trace elements lead and zinc) is well documented over major parts of the gulf. Ore mining and metal processing industries on the southwestern Iberian Peninsula started five thousand years ago and experienced a first peak during the Roman Period, which can be detected over the entire gulf. The Industrial Era added a massive, shelf-wide heavy metal excursion of unprecedented dimension. This metal contamination to the coastal ocean decreased in the 1990s and appears to be today limited to larger areas off the Tinto/Odiel and Guadiana River mouths. The unforeseen, significant finding of this study is that the gulf-wide, peak heavy metal concentration, stemming from the Industrial Era, is widely overlain by a modern sediment veneer just thick enough to cover the contaminant horizon, but thin enough to have this layer within the reach of natural or human-induced sediment mobilization events.

Potential of prodendronic polyamines with modulated segmental charge density as novel coating for fast and efficient analysis of peptides and basic proteins by CE and CE-MS.

In this work, the suitability of a new polymer family has been investigated as capillary coatings for the analysis of peptides and basic proteins by CE. This polymer family has been designed to minimize or completely prevent protein-capillary wall interactions and to modify the EOF. These coating materials are linear polymeric chains bearing as side cationizable moiety a dentronic triamine derived from N,N,N',N'-tetraethyldiethylenetriamine (TEDETA), which is linked to the backbone through a spacer (unit labeled as TEDETAMA). Four different polymers have been prepared and evaluated: a homopolymer which comprised only of those cationizable repetitive units of TEDETAMA, and three copolymers that randomly incorporate TEDETAMA together with neutral hydrosoluble units of N-(2-hydroxypropyl) methacrylamide (HPMA) at different molar percentages (25:75, 50:50 and 75:25). It has been demonstrated that the composition of the copolymers influences the EOF and therefore the separation of the investigated biopolymers. Among the novel polymers studied, poly-(TEDETAMA-co-HPMA) 50:50 copolymer was successfully applied as coating material of the inner capillary surface in CE-UV and CE-MS, providing EOF reversing together with fast and efficient baseline separation of peptides and basic proteins. Finally, the feasibility of the polymer-coated capillary was shown through the analysis of lysozyme in a cheese sample.

Determination of piroxicam by solid-phase spectrophotometry in a continuous flow system.

A simple flow injection UV spectrophotometric method was developed for the determination of piroxicam. The method is based on its transient retention and concentration on Sephadex DEAE-A-25 anion-exchange gel beads packed in the flow cell and the continuous monitoring of its native absorbance on the solid phase at 354 nm. The sample was injected into a 0.1 M NaCl carrier stream at pH 9.5 by using a simple monochannel FIA manifold. When the analytical signal reached a maximum value, piroxicam was eluted from the solid support by means of a desorbing solution (0.2 M, pH 4.5). The response of the sensor was linear in the concentration range 0.5-10 microg ml(-1) with a R.S.D. (%) of 1.8, a detection limit (3 sigma criterion) of 0.1 microg ml(-1) and a sampling rate of 13 h(-1). Application to the analysis of pharmaceutical samples testifies to the utility of this sensor. The accuracy of the proposed method was better than 5%.