Polycyclic aromatic hydrocarbons and n-alkanes in sediments of the Upper Scheldt River Basin: contamination levels and source apportionment.

The Scheldt River system is located in northern France, Belgium and the Netherlands and includes a dense network of rivers, which contributed to the urban and industrial development in this area. Three sediment cores, collected in the Upper Scheldt River (Helkijn) and two of its tributaries (the Lys River at Wervik and the Espierre Canal), were analysed for n-alkanes and polycyclic aromatic hydrocarbons (PAHs). Total n-alkane and PAH concentrations in all the sampled cores ranged from 2.8 to 29 mg kg(-1) and from 4.9 to 96 mg kg(-1), respectively. The contributions of biogenic, petrogenic and pyrolytic sources were investigated using n-alkane indexes and PAH diagnostic ratios. n-alkane chromatograms were characterized by the predominance of odd over even long chain n-alkanes (produced by terrestrial plants) and by the occurrence of a broad unresolved complex mixture (UCM) which evidenced biodegraded petroleum residues. For the three studied cores, correlations between the concentrations of UCM and n-alkanes (both expressed on an organic carbon basis) indicated a common origin or similar pathways of these allochtonous compounds to the aquatic environment. Wervik sediments were distinguished by higher n-alkane concentrations and by a major aquatic biogenic source for low molecular weight n-alkanes. The prevalence of combustion-derived PAHs was indicated by the high contribution of four, five and six rings compounds and was confirmed by isomer ratios. Higher levels of low molecular weight PAHs in Helkijn surface sediments suggested modest petrogenic inputs in this navigable canal. High PAH concentrations in Espierre sediments could be explained by a major historical contamination from urban and industrial emissions.

Determination of metal partitioning in porewater extracted from the Seine River Estuary sediment (France).

Total dissolved trace and major metals and their partitioning in porewater sediment have been investigated at two sites in the Seine River estuary (France). For this purpose, solid phase extraction (SPE) has been employed using specific chelating resins for the separation and preconcentration of organic and inorganic forms of studied metals under controlled (N2) inert atmosphere. In fact, the study is focused on the development of a method for sample collection and handling under inert atmosphere in order to avoid some potential artefacts of the extracted porewater, to preserve the samples from possible chemical oxidation changes and to determine metals partitioning between organic and inorganic forms. For this point, a separation and preconcentration method using two columns in series (chelamine and C18 columns) was used. The trace and major metals fixed on the two resins for all determinations were stripped by nitric acid (2 M) and analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Zeeman Graphite Furnace Atomic Absorption Spectroscopy (ZGF-AAS). The relationship between the distribution of metals and physico-chemical parameters such as pH and Eh (redox potential) as a function of depth was discussed. Some tendency in the distributions and seasonal variability of these traces and major metals are improved. The concentrations for all studied metals decreased as a function of depth where iron and manganese were found at mg L(-1) levels and other metals were found at [micro sign]g L(-1) levels, as well as there were significant fractions of all metals (except of manganese) which were complexed by organic matter. The comparison of data for the major elements (Fe and Mn), obtained by direct determination (without preconcentration) and preconcentration, show a very good recovery.

Influence of chloride and sediment matrix on the extractability of HgS (cinnabar and metacinnabar) by nitric acid.

The extractability of metacinnabar and cinnabar, alone or in the presence of some sediment components, with various concentrations of HNO3 (1, 4, 6, and 14 M) was studied. Both forms of HgS (0.2-0.3 mg HgS in 10-20 mL of acid) were insoluble in all HNO3 concentrations as pure compounds. The presence of FeCl3 enhanced solubility of both cinnabar and metacinnabar, especially when concentrated HNO3 was used for the extraction. As the same effect was not obtained in the presence of FeOOH, we concluded that chloride and not Fe3+ was responsible for HgS dissolution. In fact, addition of very low chloride concentration to concentrated HNO3 provoked partial (Cl>10(-4) M) or even total dissolution (Cl>10(-2) M) of HgS. In dilute HNO3 (4-6 M) cinnabar was much less affected by chloride addition than metacinnabar. Extraction of HgS by concentrated HNO3 in the presence of sediment of various salinities demonstrated that the amount of dissolved HgS increased with the increase of the sediment salinity (from freshwater to estuarine and marine sediment), confirming that chloride enhances dissolution of HgS. Removal of chloride by washing the sediment with Milli-Q water significantly reduced dissolution of added HgS during extraction by concentrated HNO3. These results demonstrate that conclusions based on the extraction schemes using concentrated HNO3 as single extractant or as the first extractant in the sequential extraction procedures can be biased. A verification of artifactual oxidation of HgS, when using more concentrated HNO3 as extractant, would help to verify reliability of the applied extraction procedure.

Determination of trace metal complexes by natural organic and inorganic ligands in coastal seawater.

It is well-documented that organic compounds form strong complexes with most metals in aquatic systems, and that seawater is a complex medium which contains a large variety of organic and inorganic ligands, including colloidal matter. We suggest that most trace metals are complexed in seawater and that some inorganic metals complexes are either labile or not stable. In contrast, metal-organic complexes are often stable and need various and specific treatments to be dissociated. In this paper we try to illustrate a good tendency of some trace metals to be complexed by organic ligands in seawater. A solid-phase extraction method was applied using a C18 column as a resin that is able to separate metals complexed by neutral organic ligands, and the chelamine resin to separate metal species that are present as labile inorganic complexes. The determination of total dissolved metal concentrations was achieved by formatting a metal-8-hydroxyquinoline complex, followed by adsorption on C18 columns and ICP-AES analysis.

Extractability of HgS (cinnabar and metacinnabar) by hydrochloric acid.

In this work we investigated the behaviour of pure HgS during extraction with dilute HCl to establish its extractability in 1 and 6 M HCl at the concentration level close to those occurring in natural sediments and soils. We found that neither cinnabar nor metacinnabar were soluble in 1 M HCl, whereas both were partially extracted by 6 M HCl. Metacinnabar precipitated in the laboratory was most prone to dissolution in 6 M HCl (up to 90%), followed by crystalline (commercial) metacinnabar (up to 70%) and cinnabar (up to 15%). Solubility of HgS in 6 M HCl was found to be dependent on its concentration, and an exponential relationship between quantity of HgS added to 20 mL of 6 M HCl (the range of 0.1-10 mg was used) and the solubility in 6 M HCl was established. For higher concentrations of HgS (10 mg in 20 mL of acid), a similarly low solubility of cinnabar was obtained as found in the literature. A study of dissolution kinetics of HgS in 6 M HCl indicated that it was a fairly slow process. Unexpected oxidation of HgS in water or 1 M HCl was found for extractions performed in Teflon vials previously used for the digestion of residual undissolved HgS by aqua regia. We presumed that the Teflon material could preserve some oxidising gases (presumably Cl(2)) developed during digestion with aqua regia which can then oxidise HgS during extraction with water or 1 M HCl. Regarding the extraction of Hg from natural sediments, we concluded that 6 M HCl could not be used to extract reactive Hg and predict bioavailability of mercury in sediments containing HgS and that experiments with model compounds should not be done at a concentration level several orders of magnitude higher than in natural samples.

Determination of trace levels of dissolved vanadium in seawater by use of synthetic complexing agents and inductively coupled plasma-atomic emission spectroscopy (ICP-AES).

In the determination of traces of dissolved vanadium in complex matrices such as seawater, separation and enrichment from the matrix is of special importance. A wide variety of methods has been proposed for preconcentration, depending to the nature of samples and the methods to be used for measurement. Among these methods separation techniques based on sorption on to chelating resins seem convenient, rapid, and capable of achieving a high concentration factor. The methods proposed in this paper are based on the transformation of all dissolved vanadium species in seawater into organic complexes by use of synthetic complexing agents such as dithizone, luminol, or 8-hydroxyquinoline; the resulting vanadium-organic complexes were sorbed on to a C(18) column at a flow rate of 5 mL min(-1). The vanadium sorbed on the C(18) columns was then stripped by use of nitric acid (2 mol L(-1)) and analysed by inductively coupled plasma-atomic emission spectroscopy, ICP-AES. This method was optimised and use of other chelating resins, such as chelamine, chelex-100, and immobilised 8-hydroxyquinoline and was compared by passing seawater samples directly over the resins. The experimental conditions (pH, acid used for elution, and contact time between the liquid sample and the resin) were optimised. The results were compared for all the resins used and were indicative of excellent and coherent reproducibility.