Seasonal variation and mixing behaviour of glutathione, thioacetamide and fulvic acids in a temperate macrotidal estuary (Aulne, NW France)

International audienceFulvic acids and two dissolved reduced sulphur substances (RSS) were analysed for one year along the whole salinity gradient in the Aulne estuary (north-western France) using differential pulse cathodic stripping voltammetry. Concentrations of glutathione-like (GSH-like), thioacetamide-like (TA-like) and fulvic acid-like (FA-like) compounds ranged from 0.2 to 38 nmol L−1, from 0.02 to 6.6 μmol L−1 and from 0.1 to 4 mgC L−1, respectively. Our results indicated primarily allochthonous-continental sources for all three compounds. The behaviour of GSH-like compounds along the salinity gradient was globally conservative, with minor losses (<25%), possibly limited due to metal complexation. TA-like compounds generally displayed non-conservative behaviour with important removals. In terms of the TA-like budget, losses were counterbalanced by exceptional inputs occurring in the flood period (February). FA-like compounds were intensely degraded (∼50%) in the last section of the river and then behaved conservatively in the estuary. The annual flux of FA-like compounds to coastal waters was 2800 ± 600 tC. This flux was mainly (74%) delivered during the high discharge period, in accordance with its known pedogenic origin

Determination of dissolved iron(III) in estuarine and coastal waters by adsorptive stripping chronopotentiometry (SCP)

International audienceAn adsorptive stripping chronopotentiometric (SCP) method has been developed for quantification of dissolved iron in estuarine and coastal waters. After UV-digestion of filtered samples the Fe(III) ions in non-deoxygenated samples were complexed with solochrom violet RS (SVRS). The complexes were then accumulated by adsorption on the surface of a mercury-film electrode. The stripping step was performed by applying a constant current of −17 μA. Sensitivity and detection limit were 15 ms nmol−1 L (270 ms μg−1 L) and 1.5 nmol L−1 (84 ng L−1), respectively, for 60-s electrolysis time. Compared with the only other chronopotentiometric method available for measurement of iron in natural waters, our procedure is fifty times more sensitive in a quarter of the electrolysis time. It therefore enables detection of the concentrations currently found in estuarine and coastal waters. The method was successfully used to study the behaviour and seasonal variations of dissolved iron in the Penzé estuary, NW France

Dissolved iron analysis in estuarine and coastal waters by using a modified adsorptive stripping chronopotentiometric (SCP) method

International audienceAn electrochemical method based on adsorptive stripping chronopotentiometry (SCP) with a rotating mercury film electrode has been developed for the determination of dissolved iron (III) at subnanomolar concentrations in estuarine and coastal waters. The detection limit was 0.11 nM after adsorption time of 60 s. Compared to the other chronopotentiometric methods available for dissolved iron measurement in natural and estuarine waters, the procedure described here exhibits a 15-fold better sensitivity. Therefore, it allows one to accurately quantify concentrations commonly found in estuarine and coastal waters. Moreover, by using the speciation scheme proposed by Aldrich and van den Berg (Electroanalysis 10 (1998) 369), several forms could be measured, i.e. reactive iron (Fe R) and reactive iron (III) (FeIII R), or estimated, i.e. complexed iron (Fe C) and reactive iron (II) (FeII R). The method described here is reliable, fast, inexpensive and compact. It was applied successfully to the study of the chemical speciation of dissolved iron along the salinity gradient of the Aulne estuary (Brittany-France)

Dynamics and source of reduced sulfur and fulvic substances in a temperate river system affected bt agriculture practices

Although reduced organic sulfur substances (RSS) as well as humic substances (HS) are widely suspected to play a role in, for example, metal speciation or used as a model of dissolved organic carbon (DOC) in laboratory studies, reports of their quantification in natural waters are scarce. We have examined the dynamics and sources of reduced sulfur, HS and DOC over an annual cycle in a river system affected by agricultural practices. The new differential pulse cathodic stripping voltammetry was successfully applied to measure glutathione-like compounds (GSHs), thioacetamide-like compounds (TAs) and the liquid chromatography coupled to organic detector to analyze HS and DOC at high frequency in the Penze River (NW France). The streamflow-concentration patterns, principal components analysis and flux analysis allowed discrimination of the source of each organic compound type. Surprisingly, the two RSS and HS detected in all samples, displayed different behavior. As previously shown, manuring practice is the main source of DOC and HS in this watershed where agricultural activity is predominant. The HS were then transferred to the river systems via runoff, particularly during the spring and autumn floods, which are responsible of >60% of the annual flux. TAs had a clear groundwater source and may be formed underground, whereas GSHs displayed two sources: one aquagenic in spring and summer probably linked to the primary productivity and a second, which may be related to bacterial degradation. High sampling frequency allowed a more accurate assessment of the flux values which were 280 tC y(-1) for DOC representing 20 kgC ha(-1) y(-1). HS, TAs and GSHs fluxes represented 60, 13, and 4% of the total annual DOC export, respectively

Stream chemical dynamic and metal accumulation in a temperate watershed affected by agricultural practices (Penzé, NW France)

RationaleUnderstanding the fate of metals in agricultural land is an important issue for agronomic sustainability. This study aimed at quantifying the export/retention of metals in a temperate watershed subject to important manuring activities. MethodsThe chemical composition of the Penze stream was examined at high resolution during a 1-year study in 2012. After immediate on-site filtration, here demonstrated as necessary to avoid modification of the dissolved-particulate partition, the concentrations of 21 elements were determined using inductively coupled plasma (ICP) optical emission spectrometry and ICP mass spectrometry. This dataset was extended with the local atmospheric deposition of several metals (Cd, Cr, Cu, Pb, Ni and Zn) monitored on a monthly basis. ResultsTwo groups were distinguished according to the evolution of the concentrations during floods. Some major cations (Na, Ca, Mg, Sr, K, Ba) and nitrate followed counter-clockwise hysteresis patterns originating from the dilution of the enriched groundwaters by surface waters. Conversely, Al, Fe, Mn, Ti, V, Cr, Co, Ni, Cu, Zn, Cd, Pb and U displayed high dissolved concentration increases at the early stage of floods due to washing out of the enriched soils. ConclusionsThe comparison of stream output fluxes for the two main inputs for the watershed, i.e. atmospheric deposition and manure spreading, indicates that the vast majority of the Cu and Zn (>99 and 96%, respectively), mainly originating from pig manure, is accumulated in the watershed. The accumulation rates for other metals were >60% for Ni and Cr, >75% for As and >90% for Pb and Cd

Annual cycle of humic substances in a temperate estuarine system affected by agricultural practices

International audienceAlthough widely studied for their chemical structures and properties (e.g., metal complexation, growth stimulation of planktonic species), humic substances (HS) have been very poorly quantified in fluvial and estuarine waters. In this monthly basis study, we determined HS concentrations (by Adsorptive Square Wave Cathodic Stripping Voltammetry) along the entire river-seawater gradient of the Penzé estuary (NW France), with the aim to characterize the export of these compounds. In this watershed where agricultural activities are predominant, manuring activities were identified as being the main source of dissolved organic carbon (DOC) and HS. HS concentrations varied usually within a narrow range in fluvial waters, i.e., 1.8 ± 0.4 mgC L−1 (150 ± 40 μM), but increased significantly as the first flood of autumn occurred (>4 mgC L−1 in river and upper estuary). At this time, HS accounted for a very high proportion of DOC (>80%). As evidenced by the increasing contribution of HS to DOC, and by the increasing contribution of small colloidal HS species; this autumnal flood increase should be attributed to a greater retention and transformation of organic matter on soils over the hotter, drier, and lighter period preceding the first autumnal flood. In the mixing zone, HS displayed mostly conservative behaviour, although some removals were occasionally observed. Overall, our study suggests that preservation of HS could be relatively important during their transfer across macrotidal temperate estuaries, at least in systems affected by agricultural practices

A comparison of in situ vs. ex situ filtration methods on the assessment of dissolved and particulate metals at hydrothermal vents

The objective of this study was to assess the impact of the filtration method (in situ vs. ex situ) on the dissolved/particulate partitioning of 12 elements in hydrothermal samples collected from the Lucky Strike vent field (Mid-Atlantic Ridge; MAR). To do so, dissolved ( <0.45 mu m) and particulate Mg, Li, Mn, U, V, As, Ba, Fe, Zn, Cd, Pb and Cu were measured using different techniques (HR-ICP-MS, ICP-AES and CCSA). Using in situ filtration as a baseline, we showed that ex situ filtration (on-board and on shore after freezing) resulted in an underestimation of the dissolved pool, which was counterbalanced by an overestimation of the particulate pool for almost all the elements studied. We also showed that on-board filtration was acceptable for the assessment of dissolved and particulate Mn, Mg, Li and U for which the measurement bias for the dissolved fraction did not exceed 3%. However, in situ filtration appeared necessary for the accurate assessment of the dissolved and particulate concentrations of V, As, Fe, Zn, Ba, Cd, Pb and Cu. In the case of Fe, on-board filtration underestimated the dissolved pool by up to 96%. Laboratory filtration (after freezing) resulted in a large bias in the dissolved and particulate concentrations, unambiguously discounting this filtration method for deep-sea chemical speciation studies. We discuss our results in light of the precipitation processes that can potentially affect the accuracy of ex situ filtration methods