Éditeur(s) : HAL CCSD IWA Publishing
Résumé : International audience
UV spectrophotometry is largely used for water and wastewater quality monitoring. The measurement/estimation of specific and aggregate parameters such as nitrate and dissolved organic carbon (DOC) is possible with UV spectra exploitation, from 2 to multi wavelengths calibration. However, if nitrate determination from UV absorbance is known, major optical interferences linked to the presence of suspended solids, colloids or dissolved organic matter limit the relevance of UV measurement for DOC assessment. A new method based on UV spectrophotometric measurement of raw samples (without filtration) coupling a dual pathlength for spectra acquisition and the second derivative exploitation of the signal is proposed in this work. The determination of nitrate concentration is carried out from the second derivative of the absorbance at 226 nm corresponding at the inflexion point of nitrate signal decrease. A short optical pathlength can be used considering the strong absorption of nitrate ion around 210 nm. For DOC concentration determination the second derivative absorbance at 295 nm is proposed after nitrate correction. Organic matter absorbing slightly in the 270-330 nm window, a long optical pathlength must be selected in order to increase the sensitivity. The method was tested on several hundred of samples from small rivers of two agricultural watersheds located in Brittany, France, taken during dry and wet periods. The comparison between the proposed method and the standardised procedures for nitrate and DOC measurement gave a good adjustment for both parameters for ranges of 2-100 mg/L NO3 and 1 30 mg/L DOC. (C) 2016 Elsevier Ltd. All rights reserved.
ISSN: 0043-1354

hal-01460742
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01460742
DOI : 10.1016/j.watres.2016.11.010
PUBMED : 27838025

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The New Jersey continental shelf extends 150 km off the shoreline. During IODP Expedition 313, siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631, 669 and 755 m below seafloor at sites 27A, 28A and 29A respectively in very shallow waters (33.5 to 36 m depth). Pore water salinities display multilayered brackish-salty-brine units 10 to 170 m thick, where low-salinity water is preferentially stored in fine-grained sediments. The sharp boundaries of these buried aquifers are often marked by cemented layers a few centimetres thick. The mineralogy and scanning electron microscope observations of these layers show two phases of cementation by authigenic minerals: (1) the early carbonate cement is frequently associated with pyrite, and (2) the late silicate cement infills the residual porosity. The isotopic compositions of the carbonate cements vary widely: −2.4 < δ¹⁸O ‰ VPDB < +2.8; −15.1 < δ¹³C ‰ VPDB < +15.6. The δ¹⁸O values indicate that the carbonate cements precipitated with pore waters comprising variable mixtures of seawater and ¹⁸O-depleted fresh water originating from submarine groundwater discharge. The δ¹³C values of the carbonate cements are related to organic matter diagenesis, providing ¹³C-depleted dissolved inorganic carbon during bacterial sulphate reduction and anaerobic oxidation of methane, and ¹³C-rich dissolved inorganic carbon during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO²-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The estimated range of temperature (18±4 °C) during carbonate precipitation is consistent with carbonate cementation at moderate burial depths; however, silicate cementation occurred later during diagenesis at deeper burial depths.
ISSN: 0276-0460

hal-01559985
https://hal.archives-ouvertes.fr/hal-01559985
DOI : 10.1007/s00367-017-0506-6

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A strong non linear relationship between nitrate and organic matter (assessed by dissolved organic carbon, DOC) has been recently demonstrated by Taylor and Townsend (2010), namely for freshwaters. In this context, our study explores this relation from the behavior of sets of normalized UV spectra (same area under each spectrum) of different water samples showing a hidden isosbestic point (HIP) around 225 nm. This HIP is linked to the existence of a simple relation between nitrate and DOC, the proportions of which vary according to the sampling location and environmental factors. In a second step, a simple linear model is proposed for nitrate-DOC relationship (α⋅NO3+β⋅DOC=1) and a validation is proposed for more than 150 samples of different Brittany rivers and lakes. For samples of the largest watershed, a complementary exploitation from data acquired during the different campaigns confirmed the seasonal evolution between spring (high nitrate/low DOC) and autumn (high DOC/low nitrate). Further investigation on other freshwater samples is needed in order to improve the limits of this linear model.
ISSN: 0045-6535

hal-01063932
https://hal.archives-ouvertes.fr/hal-01063932
DOI : 10.1016/j.chemosphere.2014.03.034
PUBMED : 24875878

Éditeur(s) : Pergamon-elsevier Science Ltd
Résumé : We report rare earth element (REE) and neodymium (Nd) isotope data for the organic fraction of sediments collected from various depositional environments, i.e. rivers (n=25), estuaries (n=18), open-ocean settings (n=15), and cold seeps (n=12). Sedimentary Organic Matter (SOM) was extracted using a mixed hydrogen peroxide/nitric acid solution (20%-H2O2 – 0.02M-HNO3), after removal of carbonate and oxy-hydroxide phases with dilute hydrochloric acid (0.25M-HCl). A series of experimental tests indicate that extraction of sedimentary organic compounds using H202 may be complicated occasionally by partial dissolution of sulphide minerals and residual carbonates. However, this contamination is expected to be minor for REE because measured concentrations in H2O2 leachates are about two-orders of magnitude higher than in the above mentioned phases. The mean REE concentrations determined in the H2O2 leachates for samples from rivers, estuaries, coastal seas and open-ocean settings yield relatively similar levels, with ΣREE = 109 ± 86 ppm (mean ± s; n=58). The organic fractions leached from cold seep sediments display even higher concentration levels (285 ± 150 ppm; mean ± s; n=12). The H2O2 leachates for most sediments exhibit remarkably similar shale-normalized REE patterns, all characterized by a mid-REE enrichment compared to the other REE. This suggests that the distribution of REE in leached sedimentary organic phases is controlled primarily by biogeochemical processes, rather than by the composition of the source from which they derive (e.g. pore, river or sea- water). The Nd isotopic compositions for organic phases leached from river sediments are very similar to those for the corresponding detrital fractions. In contrast, the SOM extracted from marine sediments display εNd values that typically range between the εNd signatures for terrestrial organic matter (inferred from the analysis of the sedimentary detrital fractions) and marine organic matter (inferred from the analysis of local surface seawater). A notable exception is the case of organic matter (OM) fractions leached from cold seep sediment samples, which sometimes exhibit εNd values markedly different from both terrigenous and surface seawater signatures. This suggests that a significant fraction of organic compounds in these sediments may be derived from chemosynthetic processes, recycling pore water REE characterized by a distinct isotopic composition. Overall, our results confirm that organic matter probably plays an important role in the oceanic REE budget, through direct scavenging and remineralization within the water column. Both the high REE abundances and the shape of shale-normalized patterns for leached SOM also suggest that OM degradation in sub-surface marine sediments during early diagenesis could control, to a large extent, the distribution of REE in pore waters. Benthic fluxes of organic-bound REE could hence substantially contribute to the exchange processes between particulates and seawater that take place at ocean margins. Neodymium isotopes could provide useful information for tracing the origin (terrestrial versus marine) and geographical provenance of organic matter, with potential applications in paleoceanography. In particular, future studies should further investigate the potential of Nd isotopes in organic compounds preserved in sedimentary records for reconstructing past variations of surface ocean circulation.
Geochimica Et Cosmochimica Acta (0016-7037) (Pergamon-elsevier Science Ltd), 2014-09 , Vol. 140 , P. 177-198

Droits : 2014 Elsevier Ltd. All rights reserved.
http://archimer.ifremer.fr/doc/00191/30250/28682.pdf
DOI:10.1016/j.gca.2014.05.016
http://archimer.ifremer.fr/doc/00191/30250/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study presents the geochemical composition of superficial sediment under oxic and suboxic bottom water conditions along the Chilean continental margin (SE Pacific), where evidence for benthic chemosynthetic activity associated with diffuse seeping of chemically reduced fluids has been reported. The exploration was carried out at: (1) the Chilean Triple Junction (CTJ), at a water depth of ∼2900 m, with the additional indication of hydrothermal activity near a methane-rich cold-seep area (46°S) (German et al., 2010); and (2) the El Quisco methane seep site (EQSS), at ∼340 m water depth (33°S) (Melo et al., 2007; Krylova et al., 2014). While the deeper CTJ is located within an oxic environment (dissolved oxygen in the bottom waters: 164 μM), the shallower EQSS lies within a suboxic environment (dissolved oxygen in bottom water: 23 μM), located within the lower limit of the SE Pacific oxygen minimum zone (OMZ).Pore water from short cores was analyzed for dissolved major, minor, and trace elements (Cl, Na, Mg, K, Ca, Sr, Si, B, P, Ba, Pb, Mn, Fe, Cd, U, and Mo), δ13DIC, sulfide, sulfate, and methane. The solid sediment fraction was likewise analyzed for total organic carbon (TOC), metals, and redox potential. Elevated sediment temperatures were found in superficial sediments (5–13 °C) at the CTJ site, which could be due to warm fluids associated with the proximity of the ridge, where hydrothermal vents may occur. Reduced fluids were also present here, indicated by higher Mn fluxes toward the water column even in oxidized sediments (RPD > 8 cm), which contrasted with the lower fluxes in reduced sediments of the EQSS site (RPD ∼ 2 cm). 13C-depleted DIC, anomalously low pore water Cl (∼15 ppb), and low concentrations of other major elements may be the result of dilution by fluid seeping and precipitation of major elements, producing authigenic enrichment (Ca, Mg, Sr). The fluid could also: (a) be diluted by pure water produced during methane hydrate dissociation, as observed in other cold-seep areas; and (b) correspond to clay mineral dehydration, as reported in plate subduction systems. The reducing conditions established at the CTJ conduct the Cd enrichment at a similar magnitude of that seen at the shallower suboxic site (EQSS). Evidence of chimney or vent fauna was not observed. At the EQSS, higher TOC and total sulfide contents were consistent with enhanced deposition of organic matter and reducing conditions developed in the OMZ, favoring the authigenic enrichment of Cd, U and Pb. The geochemical evidence, based only on methane concentrations and δ13DIC, is insufficient to establish the presence of methane seeps, as previously reported.
ISSN: 0079-6611

hal-01412700
https://hal.archives-ouvertes.fr/hal-01412700
DOI : 10.1016/j.pocean.2016.09.002

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Coastal aquifers often display seawater intrusion resulting in the formation of a salty water wedge progressing inland. This study investigates the mass transfers in the mixing zone at the freshwater-seawater interface where the water is out of equilibrium with the rock-forming carbonates. Investigations were conducted in two boreholes, separated by 5 m, at the Ses Sitjoles test site (Mallorca Island, Spain) where repeated electrical conductivity logs of the formation and the saturating fluid, as well as regular pore-water sampling and permanent downhole multi-parameter monitoring of the water were performed over a period of 9 a. In the mixing zone, the significant acidification, the calcite saturation index profile and the Ca concentration profile cannot be explained by conservative mixing nor by dissolution-precipitation reactions only. Conversely, the analysis of organic C content and of the distinctly different time-resolved pH profiles measured in the two boreholes suggests the development of perennial biomass that triggers calcite dissolution. Moreover, the presence of biomass seems to be correlated with the permeability and vertical connectivity at the meter-scale. It is speculated that the mechanism could be self-activated because the microbiological activity induces calcite dissolution and tends to increase porosity and permeability that favors biomass development.
ISSN: 0883-2927

hal-00937665
https://hal.archives-ouvertes.fr/hal-00937665
DOI : 10.1016/j.apgeochem.2013.09.011

Éditeur(s) : HAL CCSD Elsevier
Résumé : This study analyzes the records of several trace metals sensitive to redox conditions in continental shelf sediments off Concepcion, Chile (36 degrees S). The continental margin off Concepcion (36 S; 73 W) lies beneath an important upwelling center characterized by high primary production rates and, consequently, high fluxes of organic matter. In spring and summer, this material settles to the seafloor where it decays, producing periods of very low oxygen content in bottom waters (<1 mL L-1). In addition, an oxygen minimum zone develops at similar to 100-400 m water depth, where dissolved oxygen levels are <0.5 mL L-1. This situation changes during strong El Nino events, when dissolved oxygen at the bottom increases drastically (>1 mL L-1).;The goals of this study were to determine the input of trace metals to the sediment and to decipher how this information can be used to reveal variations in primary productivity or bottom oxygenation. Gravity cores collected at two stations - VG06-2 over the mid-shelf station (88 m water depth, upper boundary of the oxygen minimum zone) and VG06-3 over the outer shelf (120 m water depth, within the oxygen minimum zone) - were sampled for high resolution profiles (1 cm) of trace metals, biogenic opal, stable isotopes, and total organic carbon. The results suggest that the variability in the trace metal distribution on the continental shelf off Concepcion is determined by redox conditions and the organic carbon flux to the bottom. Some sections of the sediment cores from the outer shelf showed appreciable authigenic enrichment of U, Cd, and Mo (EF: 5-10, 2-5, and 10-16 respectively) along with heavier values of delta N-15, suggesting periods of suboxic conditions. During these periods, fluxes of organic material to the bottom were higher, as indicated by elevated TOC and opal contents. Alternating periods of higher and lower trace metal contents were not observed mid-shelf as they were on the outer shelf. Rather, the mid-shelf samples showed authigenic enrichment of U, Cd, and Mo (EF: 1-6, 4-5, and 10-20, respectively) throughout the core except in a 10-cm-thick gray layer. In general, authigenic enrichment of U. Mo, and Cd occurred at both sites, coincident with olive green layers in the cores. These layers were associated with periods of elevated primary productivity and suboxic conditions. Such periods did not seem to last as long as the oxygenated periods, which had higher inputs of refractive detrital material, coincident with the occurrence of distinct gray sediment layers.
ISSN: 0079-6611

hal-00682159
https://hal.archives-ouvertes.fr/hal-00682159
DOI : 10.1016/j.pocean.2011.07.010

Éditeur(s) : HAL CCSD AGU and the Geochemical Society
Résumé : International audience
[1] Large changes in magnetic mineral concentration dependent parameters by more than 1 order of magnitude occur over 50–150 cm intervals in two marine sediment cores from the oxygen minimum zone in the Gulf of Aden. High-resolution sedimentological and chemical analyses indicate that these intervals are not associated with turbiditic events or sediment reworking, they do not result from changes in carbonate dilution or differences in sediment properties, and they do not correspond to volcanic layers. Magnetic mineralogical analyses reveal a change in magnetic mineral concentration from a magnetite-goethite assemblage to pure magnetite within the peak. The peaks almost disappear when the abundance of magnetic minerals is calculated after correcting for the magnetic moments of each magnetic mineral. Therefore, under the assumption that the variability of the magnetic parameters results from postdepositional mineralogical transformations, a relatively constant amount of magnetite was present at the surface of the sediment. Changes in redox conditions and nonsteady state diagenesis transformations have effectively been observed along both cores. Large values of total organic carbon coincide with poor preservation of biogenic and detrital magnetite, which reflects reductive dissolution of the finer magnetite grains. At the same levels, Fe 2þ release from reductively dissolved magnetite favored precipitation of goethite. The susceptibility peaks coincide with episodes of magnetite preservation caused by reduced surface
ISSN: 1525-2027

insu-01311064
https://hal-insu.archives-ouvertes.fr/insu-01311064
https://hal-insu.archives-ouvertes.fr/insu-01311064/document
https://hal-insu.archives-ouvertes.fr/insu-01311064/file/ggge2013-14-3779-bouilloux.pdf
DOI : 10.1002/ggge.20234

Éditeur(s) : Elsevier
Résumé : The main feature of the Congo-Angola margin in the Gulf of Guinea is the Congo (ex-Zaire) deep-sea fan composed of a submarine canyon directly connected to the Congo River, a channel and a [sediment] lobe area. During the multi-disciplinary programme called BIOZAIRE conducted by Ifremer from 2000 to 2005, two CTD-O2 sections with discrete water column samples were performed (BIOZAIRE3 cruise: 2003-2004) to study the influence of the Congo River discharges, both in the surface layer and in the deep and near-bottom layers. The surface layer water is greatly diluted with river water that has a heavy particle load. The deep layer is affected by episodic turbidity currents that flow in the deep Congo channel and reach deep areas far from the coast. Previous studies revealed deep anomalies in oxygen (deficit) and nutrient (excess) concentrations at not, vert, similar4000 m depth and assumed that they resulted from mineralisation of the particulate organic matter from the Congo River. The BIOZAIRE3 sections were designed to explore these phenomena in more detail near the Congo channel. Oxygen and nutrients were measured as well as additional parameters, including stable isotopes of oxygen and carbon, dissolved inorganic carbon and pH. For the surface layer, the effect of the Congo River was studied with reference to salinity. Deviations from the theoretical dilution of various inorganic solutes suggested the occurrence of mineralisation and consumption processes. For the deep layer, the network of CTD-O2 stations gave a more detailed description of the deep anomalies than in previous studies. From the east-west section, anomalies appeared on the bottom at 4000 m depth and became slightly shallower when they spread to the west. They were also present north and south on the bottom along the 4000 m isobath. In these deep waters, the decrease in the o13C values of dissolved inorganic carbon confirmed that the mineralisation of organic matter plays a role in generating these anomalies. The location of the origin of this deep anomaly is debated. Here, arguments are given in favour of mineralisation of the particulate organic matter input that overflows from the Congo channel at not, vert, similar4000 m depth during turbidity current events. Other authors suggest that this input comes from downslope particle transport. Anomalies of the same origin, but weaker, also occurred deeper on the Congo lobe, where the Congo channel ends, but with a significant pH decrease on the bottom which was not seen at 4000 m depth.
Deep Sea Research Part II: Topical Studies in Oceanography (0967-0645) (Elsevier), 2009-11 , Vol. 56 , N. 23 , P. 2183-2196

Droits : 2009 Elsevier Ltd All rights reserved.
http://archimer.ifremer.fr/doc/2009/publication-6737.pdf
DOI:10.1016/j.dsr2.2009.04.002
http://archimer.ifremer.fr/doc/00000/6737/

Éditeur(s) : HAL CCSD IWA Publishing
Résumé : International audience
Anti-cancer drugs are an important class of pharmaceutical products. Methotrexate (MTX) is a folic acid antagonist used in high doses as antimetabolite in anti-cancer treatment as well as in low doses for the treatment of rheumatoid arthritis and adults' psoriasis. In the past, several anti-cancer drugs, including methotrexate, have been found in the environment. Their presence in water, especially if used for the production of drinking water, is even in low concentrations of particular interest, due to the risk to retrieve them in the consumed water and their high activity and grave effects. But prior to usage as drinking water, raw waters are treated and chlorination is a common practice in several countries. As such a treatment can lead to the formation of organochlorine in water, the study of the fate of MTX during chlorination in a batch trial was carried out. The reaction was monitored by dissolved organic carbon (DOC) and by fluorescence and UV spectroscopy. Investigation of by-products formed was done with liquid chromatography/mass spectrometry (LC/MS). Under the given experimental conditions, Methotrexate was eliminated rapidly (t1/2 around 21 min). However, DOC elimination was incomplete. Monitoring with LC-MS showed the formation of a monochlorinated transformation product of MTX. In silico analysis of the proposed transformation products for different carcinogenic, mutagenic and genotoxic endpoints with different software platforms provided no clear evidence that the possible transformation products after chlorination might be more toxic than the parent compound. However, since a number of alerts is altered after chlorination, it cannot be excluded that the toxicity of these transformation products might be modulated compared with the parent compound.
ISSN: 0043-1354

hal-01016617
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01016617
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01016617/document
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01016617/file/Monitoringsur methotrexate_final.pdf
DOI : 10.1016/j.watres.2014.03.008