Synthetic green rusts, GRs, are prepared by oxidation of Fe(OH)2 incorporating Cl-, SO4 2-, or CO3 2- ions. E h−pH diagrams are drawn, and thermodynamic data are derived. A GR incorporating OH- ions, GR1(OH-), is suspected to exist like similar other M(II)−M(III) compounds. GRs form as corrosion products of steels, implying microbially induced corrosion. Mössbauer and Raman spectroscopies allowed the identification of GR in samples extracted from hydromorphic soils scattered over Brittany, France. This mineral has a varying Fe(III)/Fe(II) ratio. At Fougères, it increases with depth till the oc currence of more oxidized ferric oxyhydroxide. In the same sites, soil solutions are collected and prevented from any oxidation and photoreduction. In large ranges of pH, pe, and Fe(II) concentration variations, soil solutions are in equilibrium with a Fe(II)−Fe(III) compound, a GR1 mineral with pyroaurite-like structure incorporating OH- ions and having the formula [FeII (1 - x )FeIII x (OH)2]+ x ·[xOH]- x ≡ Fe(OH)(2+ x ). Computation of ionic activity products (IAP) of the equilibria between minerals and solutions leads to molar ratio x from 1/3 to 2/3, in agreement with the Fe(III)/Fe(II) ratios obtained from Mössbauer spectroscopy. The GR mineral plays a key role for controlling iron in soil solutions, and equilibria between soil and suspension constrain the Fe(III)/Fe(II) ratios of the iron(II)−iron(III) hydroxide.

International audienceIncreasing dissolved organic carbon (DOC) concentrations have been reported during the last 15 years in streams from the United Kingdom, Northern Europe and North America. Identifying the sources of DOC and the controls of the delivery to the stream is important to understand the significance of these trends. This relies on the availability of observations of DOC dynamics during storm events, since much of the DOC export from soils to streams occurs during high flows. This study analyses DOC data for eight storm events during winter 2005-2006 in a small agricultural experimental catchment - the Kervidy-Naizin experimental catchment - located in Western France. A four end-member mixing approach was applied to the eight monitored storm events to identify DOC sources and quantify their respective contribution to DOC stream fluxes, using DOC, nitrate, sulphate and chloride as tracers. The results show that DOC concentrations in the stream at the outlet of this catchment increase markedly during storm events. The slope of the linear regression between DOC concentration and discharge was not constant for the eight events and depended on pre-event hydrological conditions. Between 64 and 86% of the DOC that enter the stream during storms originated from the upper layers of the riparian wetland soils. The variation of the delivery of DOC seems to be controlled by hydrological processes only, the wetland soils acting as a non-limiting store

[1] To obtain better constraints on the control of seasonal hydrological variations on dissolved organic carbon (DOC) dynamics in headwater catchments, we combined hydrometric monitoring with high-frequency analyses of DOC concentration and DOC chemical composition (specific UV adsorption, 13 C) in soil and stream waters during one complete hydrological cycle in a small lowland catchment of western France. We observed a succession of four hydrological periods, each corresponding to specific DOC signatures. In particular, the rise of the upland water table at the end of the rewetting period yielded to a strong increase of the specific UV absorbance (from 2.5 to 4.0 L mg C À1 m À1 ) and of the 13 C values (from À29 to À27%) of the soil DOC. Another striking feature was the release of large amounts of DOC during reduction of soil Fe-oxyhydroxides at the end of the highflow period. Comparison of hydrometric data with DOC composition metrics showed that soils from the upland domains were rapidly DOC depleted after the rise of the water table in these domains, whereas wetland soils acted as quasi-infinite DOC sources. Results from this study showed that the composition and ultimate source of the DOC exported to the stream will depend on the period within the annual hydrological cycle. However, we found that the aromatic DOC component identified during the high-flow period will likely represent the dominant DOC component in stream waters on an annual basis, because most of the annual stream DOC flux is exported during such periods.Citation: Lambert, T., A.-C. Pierson-Wickmann, G. Gruau, A. Jaffrezic, P. Petitjean, J.-N Thibault, and L. Jeanneau (2013), Hydrologically driven seasonal changes in the sources and production mechanisms of dissolved organic carbon in a small lowland catchment, Water Resour. Res., 49,[5792][5793][5794][5795][5796][5797][5798][5799][5800][5801][5802][5803]

Abstract. High-frequency, long-term and multisolute measurements are required to assess the impact of human pressures on water quality due to (i) the high temporal and spatial variability of climate and human activity and (ii) the fact that chemical solutes combine short-and long-term dynamics. Such data series are scarce. This study, based on an original and unpublished time series from the Kervidy-Naizin headwater catchment (Brittany, France), aims to determine solute transfer processes and dynamics that characterise this strongly human-impacted catchment.The Kervidy-Naizin catchment is a temperate, intensive agricultural catchment, hydrologically controlled by shallow groundwater. Over 10 yr, five solutes (nitrate, sulphate, chloride, and dissolved organic and inorganic carbon) were monitored daily at the catchment outlet and roughly every four months in the shallow groundwater.The concentrations of all five solutes showed seasonal variations but the patterns of the variations differed from one solute to another. Nitrate and chloride exhibit rather smooth variations. In contrast, sulphate as well as organic and inorganic carbon is dominated by flood flushes. The observed nitrate and chloride patterns are typical of an intensive agricultural catchment hydrologically controlled by shallow groundwater. Nitrate and chloride originating mainly from organic fertilisers accumulated over several years in the shallow groundwater. They are seasonally exported when upland groundwater connects with the stream during the wet season. Conversely, sulphate as well as organic and inorganic carbon patterns are not specific to agricultural catchments. These solutes do not come from fertilisers and do not accumulate in soil or shallow groundwater; instead, they are biogeochemically produced in the catchment. The results allowed development of a generic classification system based on the specific temporal patterns and source locations of each solute. It also considers the stocking period and the dominant process that limits transport to the stream, i.e. the connectivity of the stocking compartment. This mechanistic classification can be applied to any chemical solute to help assess its origin, storage or production location and transfer mechanism in similar catchments.

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The microbiological quality of coastal or river waters can be affected by faecal pollution from human or animal sources. An efficient MST (Microbial Source Tracking) toolbox consisting of several host-specific markers would therefore be valuable for identifying the origin of the faecal pollution in the environment and thus for effective resource management and remediation. In this multidisciplinary study, after having tested some MST markers on faecal samples, we compared a selection of 17 parameters corresponding to chemical (steroid ratios, caffeine, and synthetic compounds), bacterial (host-specific Bacteroidales, Lactobacillus amylovorus and Bifidobacterium adolescentis) and viral (genotypes I-IV of F-specific bacteriophages, FRNAPH) markers on environmental water samples (n = 33; wastewater, runoff and river waters) with variable Escherichia coli concentrations. Eleven microbial and chemical parameters were finally chosen for our MST toolbox, based on their specificity for particular pollution sources represented by our samples and their detection in river waters impacted by human or animal pollution; these were: the human-specific chemical compounds caffeine, TCEP (tri(2-chloroethyl)phosphate) and benzophenone; the ratios of sitostanol/coprostanol and coprostanol/(coprostanol+24-ethylcopstanol); real-time PCR (Polymerase Chain Reaction) human-specific (HF183 and B. adolescentis), pig-specific (Pig-2-Bac and L. amylovorus) and ruminant-specific (Rum-2-Bac) markers; and human FRNAPH genogroup II.