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

RATIONALE: Understanding 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. METHODS: The chemical composition of the Penzé 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. RESULTS: Two 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. CONCLUSIONS: The 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.

On the control of copper colloidal distribution by humic substances in the Penzé estuary.

In this study, we investigated the variations of colloidal Cu in a temperate macrotidal estuarine system (Penzé, NW France). The originality of this work resides on examining seven colloidal/dissolved fractions at seven different periods of the year whereas previous studies on estuaries generally considered two or three fractions and were focused on a unique survey. A high proportion of Cu (∼90%) was generally found as colloids (5 kDa-0.45 µm) throughout the salinity gradient with divergent size distributions being observed over the seasonal cycle. This consisted essentially in two contrasted periods, i.e. winter-spring with a greater association of Cu with high molecular weight (HMW) compounds (50 kDa-0.45 µm) and summer-autumn with Cu being found mainly as low molecular weight (LMW) forms (5-50 kDa). The comparison of Cu with humic substances (HS) data allowed to us to highlight the importance of the pedogenic refractory organic matter in controlling the concentrations and the size distribution of Cu in the estuary. In the mixing zone, Cu behaved conservative in autumn and winter but important additions of HMW compounds were observed in spring in the lower estuary as the result of particulate organic matter degradation in the sediment. Although HS appears to be the background chelators of Cu in the systems, the strong benthic inputs occurring in spring may be of different (biotic) origin and may be in part responsible for the higher association of Cu with HMW compounds.

Simple and simultaneous determination of glutathione, thioacetamide and refractory organic matter in natural waters by DP-CSV.

Although reduced sulphur substances, such as thiol compounds, contain extremely reactive functional groups in the cell, and influence metal speciation and solubility, very few techniques have been developed to quantify such substances in natural waters. In this paper we present a novel method that allows for the simultaneous identification and quantification of glutathione (GSH), thioacetamide-like compounds (TA), and refractory organic matter (ROM) by differential pulse cathodic stripping voltammetry (DP-CSV). Organic compounds are initially deposited on a mercury drop electrode at 0.000 V, pH 1.95, in the presence of ~200 nmol L(-1) Mo(VI), and then stripped, creating reduction peak currents at specific potentials. Using a 60-s deposition time, limits of detection (LODs) are 1 nmol L(-1), 81 nmol L(-1) and 14 µg C L(-1) for GSH, TA and ROM, respectively. By increasing the deposition time to 300 s, LOD is decreased to 0.2 nmol L(-1), 22 nmol L(-1) and 2 µg C L(-1), respectively. This method has a number of advantages in terms of its rapidity, low cost, and relative simplicity (due to the lack of derivatization and pre-concentration steps) and is also an effective method for simultaneously analysing GSH, TA and ROM in water. When not mixed in solution, GSH, L-cysteine and N-acetyl-L-cysteine, as well as TA-like compounds and thiourea, can be detected and identified by measuring their peak potential and standard addition, due to the acidic pH, which also allows for a longer preservation of the filtered sample. The new method described in this paper was tested along an entire river-seawater gradient of the Aulne Estuary (Brittany, France) to assess its capability in terms of determining these natural organic compounds in various surface waters.

Sulfide determination in hydrothermal seawater samples using a vibrating gold micro-wire electrode in conjunction with stripping chronopotentiometry.

A rapid electrochemical stripping chronopotentiometric procedure to determined sulfide in unaltered hydrothermal seawater samples is presented. Sulfide is deposited at -0.25 V (vs Ag/AgCl, KCl 3M) at a vibrating gold microwire and then stripped through the application of a reductive constant current (typically -2 µA). The hydrodynamic conditions are modulated by vibration allowing a short deposition step, which is shown here to be necessary to minimize H(2)S volatilization. The limit of detection (LOD) is 30 nM after a deposition step of 7s. This LOD is in the same range as the most sensitive cathodic voltammetric technique using a mercury drop electrode and is well below those reported previously for other electrodes capable of being implemented in situ.

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

An 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 60s. 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) (Fe(III) R), or estimated, i.e. complexed iron (Fe C) and reactive iron (II) (Fe(II) 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).

A stripping chronopotentiometric (SCP) method with a gold film electrode for determining inorganic arsenic species in seawater.

An electrochemical method based on stripping chronopotentiometry (SCP) with a gold film electrode has been developed for determining arsenic in seawater. The detection limits were 0.053 ppb (0.71 nM) and 0.022 ppb (0.29 nM) for total inorganic As (As(T)) and As(III) after deposition times of 60 and 150 s, respectively. Compared to other stripping chronopotentiometric methods that use a gold macroelectrode to perform measurements of arsenic in seawater, the procedure described here exhibits better sensitivity and a fourfold shorter deposition time. Among the SCP methods, our procedure had proven its ability to analyse arsenic(III) in seawater. It therefore allows the concentrations of the various arsenic inorganic species in seawater--i.e. As(T), As(III) and As(V)--to be analysed. The proposed method is reliable, inexpensive and compact. It was successfully applied to the study of arsenic speciation along the salinity gradient of the Penzé estuary (NW France).

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

An 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 microA. Sensitivity and detection limit were 15 ms nmol(-1) L (270 ms microg(-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.

Measurement of total selenium and selenium(IV) in seawater by stripping chronopotentiometry.

We developed a stripping chronopotentiometric method (constant current stripping analysis, CCSA) with a mercury film electrode for selenium quantification in seawater. A sensitivity and detection limit of 222 ms ng(-1) l and 4 ng l(-1) (50 pM), respectively, were accomplished for a 3-min electrolysis time. Compared to the other chronopotentiometric methods available for a single selenium measurement only in natural waters, our procedure exhibits a ten times better sensitivity. It, therefore, allows one to reach the current concentration thresholds found in coastal and oceanic waters (30-200 ng l(-1)). Moreover, a simple change in operating conditions enables one to also quantify Se(IV), a toxic dissolved species. With respect to the other electrochemical methods of current use, our procedure is beneficial because of its ease-of-use: it needs neither degassing step, nor catalyser.