Cold vapour generation electrothermal atomic absorption spectrometry and solid phase extraction based on a new nanosorbent for sensitive HG determination in environmental samples (sea water and river water)

Mercury is not an essential element for plant or animal life and it is a potential environmental toxic because of its tendency to form covalent bonds with organic molecules and the high stability of the Hg-C bond. Reports estimate a total mercury concentration in natural waters ranging from 0.2 to 100 ng L-1. Due to this fact, highly sensitive methods are required for direct determination of such extremely low levels. In this work, a rapid and simple method was developed for separation and preconcentration of mercury by flow injection solid phase extraction coupled with on-line chemical vapour generation electrothermal atomic absorption spectrometry. The system is based on chelating retention of the analyte onto the mini column filled with a mesoporous silica functionalized with 1,5 bis (di-2-pyridyl) methylene thiocarbohydrazide. The main aim of this work was to develop a precise and accurate method for the determination of the Hg. Under the optima conditions and 120 s preconcentration time, the detection limit obtained was 0.009 μg L-1, with RSDs 3.7 % for 0.2 μg L-1, 4.8 % for 1 μg L-1 and enrichment factor 4, Furthermore, the method proposed has permitted the determination of Hg with a reduction in the analysis time, the sample throughput was about 18 h-1, low consumption of reagents and sample volume. The method was applied to the determination of Hg in sea water and river water. For the quality control of the analytical performance and the validation of the newly developed method, the analysis of two certified samples, TMDA 54.4 Fortified Lake, and LGC6187 River sediment was addressed. The results showed good agreement with the certified values.

Heat fluxes between the Guadalquivir river and the Gulf of Cádiz Continental Shelf

An 18-year time series of daily sea surface temperature of Gulf of Cadiz and an 18-month time series of temperature collected in the vicinity of the Guadalquivir estuary mouth have been analyzed to investigate the heat exchange between the estuary and the adjacent continental shelf. The first time identifies a continental shelf area where seasonal thermal oscillation signal (amplitudes and phase) changes abruptly. In order to explain this anomaly, the second data set allows a description of thermal fluctuations in a wide range of frequencies and an estimation of the upstream heat budget of the Guadalquivir estuary. Results show that high frequency thermal signal, diurnal and semidiurnal, and water flux signal through Guadalquivir mouth, mainly semidiurnal, apparently interact randomly to give a small exchange of thermal energy at high frequency. There is no trace, at the estuary's mouth, of daily heat exchanges with intertidal mudflats probably because it tends to cancel on daily time scales. Results also show that fluctuations of estimated air-sea fluxes force fluctuations of temperature in a quite homogeneous estuarine, with a delay of 20 days. The along-channel thermal energy gradient reaches magnitudes of 300-400 J m-4 near the mouth during the summer and winter and drives the estuary-shelf exchange of thermal energy at seasonal scale. Particularly, the thermal heat imported by the estuary from the shelf area during late fall-winter-early spring of 2008/2009 is balanced by the thermal heat that the estuary exports to the shelf area during late spring-summer of 2008. In summary, Guadalquivir river removes/imports excess of thermal energy towards/from the continental shelf seasonally, as a mechanism to accommodate excess of heat from one side respect to the other side.