Phosphate buffering in mangrove sediment pore water under eutrophication and deforestation influences.

Phosphorus (P) behavior was evaluated in mangrove wetlands impacted by urban sewage, including a deforested site. Sediment cores were analyzed for grain size, organic carbon, total nitrogen, stable isotopes (δ13C and δ15N), P contents, and pore water PO43- concentrations and net consumption/production rates. Under stronger eutrophication influence, significantly higher P (1390 vs. <1000 µg/g), δ15N (8.9 vs. <6.7 ‰) and algal material contents (with lower C/N ratio and heavier δ13C) occurred. Depth-integrated PO43- consumption rates in eutrophicated sites were up to two orders of magnitude higher (at the deforested site) than in a moderately preserved mangrove. The whole core of the moderately preserved site presented no saturation of PO43- buffering capacity, while more eutrophicated sites developed buffering zones saturated at ∼18-26 cm depth. Contrasting to nearby subtidal environments, eutrophication did not cause larger pore water PO43- concentration, evidencing the role of PO43- buffering on P filtering by mangrove wetlands.

Two-Dimensional Mapping of Arsenic Concentration and Speciation with Diffusive Equilibrium in Thin-Film Gels.

We present a new approach combining diffusive equilibrium in thin-film gels and spectrophotometric methods to determine the spatial distribution of arsenite, arsenate, and phosphate at submillimeter resolution. The method relies on the simultaneous deployment of three gel probes. Each retrieved gel is exposed to malachite green reagent gels differing in acidity and oxidant addition, leading to green coloration dependent on analyte speciation and concentration. Hyperspectral images of the gels enable mapping the three analytes in the 2.5-20 µM range. This method was applied in a contaminated brook in the Harz mountains, Germany, together with established mapping of dissolved iron. The use of two-dimensional (2D) gel probes was compared to traditional porewater extraction. The gels revealed banded porewater patterns on a mm-scale, which were undetectable using traditional methods. Small-scale correlation analyses of arsenic and iron microstructures in the gels suggested active iron-driven local redox cycling of arsenic. Overall, the results indicate continuous net release of arsenic from contaminant particles and deepen our understanding of arsenate transformation under anaerobic conditions. This study is the first fine-scale 2D characterization of arsenic speciation in porewater and represents a crucial step toward understanding the transfer and redox cycling of arsenic in contaminated sediment/soil ecosystems.

Drivers for primary producers' dynamics: New insights on annual benthos pelagos monitoring in anthropised freshwater marshes (Charente-Maritime, France).

Wetlands, especially marshes, support many services such as carbon catchment control or water purification led by primary producers such as phytoplankton and microphytobenthos (PB). The impact of the sedimentary compartment, as source and sink of essential nutrients for the water column, is often neglected in the study of their dynamics and water purification capacity of the systems. This work compared monthly (between February 2020 and April 2021) the benthic and pelagic primary producers' dynamics in two anthropised freshwater marshes (Marans and Genouillé), with the simultaneous follow-up of physico-chemical parameters of the water column and nutrient fluxes at the sediment-water (SWI) interface. It was suggested a strong contribution of phytoplankton (pumping) and the benthic compartment (denitrification) to the water purification of these two nitrates (NO3-)-rich marshes. Total phytoplankton production fluctuated between ∼5 (winter) and 1500 mg C m-3 d-1 (fall) at Marans and between 40 (winter) and ∼750 mg C m-3 d-1 (spring) at Genouillé. At Marans, soluble reactive phosphorus (SRP) benthic effluxes (-2.101 to -6.102 µmol m-2 d-1 in fall and summer, respectively) coincided with phytoplankton bloom periods. These effluxes were inhibited by NO3- penetration in the sediment (0 to 5.104 µmol m-2 d-1), by inhibiting iron respiration. At Genouillé, inhibition of SRP effluxes depended on denitrification rate and on P stocks in the sediment, where slight SRP effluxes (-101 µmol m-2 d-1) could have co-occurred with slight NO3- influxes (5.102 µmol m-2 d-1) in spring. The presence of PB (between 10-60 and 40-120 mg gsed-1 at Marans and Genouillé, respectively), suggested a strong contribution of the benthic compartment to the total primary production (benthic and pelagic through resuspension processes) in these environments. This work encourages to consider the benthos and the pelagos as a unicum to provide better sustainable management of such systems and limit eutrophication risks in coastal areas.

Coupling between sediment biogeochemistry and phytoplankton development in a temperate freshwater marsh (Charente-Maritime, France): Evidence of temporal pattern.

In freshwater systems, sediment can be an important source for the internal loading of PO4. The limiting character of this element in such system leads to consider this phenomenon in terms of eutrophication risks and water quality stakes. A four-months follow-up (January, March, April and May 2019) was carried out in a strong phosphate (PO4) limited secondary channel from an artificial irrigation system of Charente Maritime (France) to link the mobilization of remineralization products in the upper 6 cm layer of sediment (conventional core slicing/centrifugation and DET probes) and the phytoplankton biomass dynamics in the water column. Results showed congruent patterns between the temporal succession of the organic matter mineralization processes in the sediment and the primary biomass dynamics in the water column. In January and March (considered in winter), PO4 proved to be retained by adsorption onto iron oxides in anoxic sediment since pore water nitrate inhibited for about a month the respiration of metal oxides in the first cm of sediment, thus limiting PO4 availability and the phytoplankton growth. In April and May (early spring), after exhaustion of pore water nitrate, the dissolutive reduction of iron oxides released PO4 into pore water generated a significant diffusive outgoing flux from the sediment to the water column with a maximum in April (-1.10E-04±2.81E-05 nmol cm-2 s-1). This release coincided with the nanophytoplankton bloom (5.50 µg Chla L-1) and a potential increase of PO4 concentration in the water column. This work provides some insight on the importance of benthic-pelagic coupling in anthropogenic systems. This conceptual model has to be deployed on other sites of interest where internal loading of P takes precedence over external inputs and nitrate mitigation drives its benthic recycling and ultimately its bioavailability. This is to be essential to characterize the aquatic environment quality in order to limit eutrophication risks.

Assessment of the metal contamination evolution in the Loire estuary using Cu and Zn stable isotopes and geochemical data in sediments.

In this work, a multi-elemental approach combining Cu and Zn stable isotopes is used to assess the metal contamination evolution in the Loire estuary bulk sediments. Elemental geochemical data indicate an increase of metal concentrations from the beginning of the industrial period peaking in the 1990s, followed by an attenuation of metal contamination inputs to the estuary. Zinc isotope compositions suggest a binary mixing process between Zn derived from terrigenous material and multi-urban anthropogenic sources. Copper isotope systematics indicate a single natural dominant source represented by weathered silicate particles from soils and rocks. This work demonstrates the applicability of Zn isotopes to identify anthropogenic Zn sources in coastal systems, even under a low to moderate degree of contamination. Further studies are required to constrain Cu sources and to elucidate possible effects of grain-size and mineralogy in the Cu isotope composition of sediment in the Loire estuary.

Two-dimensional ammonium distribution in sediment pore waters using a new colorimetric diffusive equilibration in thin-film technique.

This study presents a new gel based technique to describe the pore water ammonium distribution through the sediment-water interface in two dimensions at a millimeter scale. The technique is an adaptation of the classical colorimetric method based on the Berthelot's reaction. After the thin film of the gel probe was equilibrated by diffusion either in standard solutions or in pore waters, a colorimetric reagent gel was set on the gel probe, allowing development of the characteristic green color. A flatbed scanner and subsequent densitometry image analysis allowed to determine the concentration distribution of ammonium. The gel probe was tested in the laboratory for two media, deionized water and seawater, within the range 0-3000 µM in NH4 +. Detection limit is about 20 µM and accuracy about ±25 µM. The field validation was realized in a tidal mudflat of the French Atlantic coast by comparison with conventional pore water extraction and colorimetric analysis. The large range of concentrations and its applicability in continental and marine sediments suggest a wide range of applications of the technique for a reasonable cost.

Response of a kleptoplastidic foraminifer to heterotrophic starvation: photosynthesis and lipid droplet biogenesis.

The aim of this work is to document the complex nutritional strategy developed by kleptoplastic intertidal foraminifera. We study the mixotrophic ability of a common intertidal foraminifer, Elphidium williamsoni, by (i) investigating the phylogenetic identity of the foraminiferal kleptoplasts, (ii) following their oxygenic photosynthetic capacity and (iii) observing the modification in cellular ultrastructural features in response to photoautotrophic conditions. This was achieved by coupling molecular phylogenetic analyses and TEM observations with non-destructive measurements of kleptoplast O2 production over a 15-day experimental study. Results show that the studied E. williamsoni actively selected kleptoplasts mainly from pennate diatoms and had the ability to produce oxygen, up to 13.4 nmol O2 cell-1 d-1, from low to relatively high irradiance over at least 15 days. Ultrastructural features and photophysiological data showed significant differences over time, the number of lipid droplets, residual bodies and the dark respiration increased; whereas, the number of kleptoplasts decreased accompanied by a minor decrease of the photosynthetic rate. These observations suggest that in E. williamsoni kleptoplasts might provide extra carbon storage through lipid droplets synthesis and highlight the complexity of E. williamsoni feeding strategy and the necessity of further dedicated studies regarding mechanisms developed by kleptoplastidic foraminifera for carbon partitioning and storage.

Kleptoplastidic benthic foraminifera from aphotic habitats: insights into assimilation of inorganic C, N and S studied with sub-cellular resolution.

The assimilation of inorganic compounds in foraminiferal metabolism compared to predation or organic matter assimilation is unknown. Here, we investigate possible inorganic-compound assimilation in Nonionellina labradorica, a common kleptoplastidic benthic foraminifer from Arctic and North Atlantic sublittoral regions. The objectives were to identify the source of the foraminiferal kleptoplasts, assess their photosynthetic functionality in light and darkness and investigate inorganic nitrogen and sulfate assimilation. We used DNA barcoding of a ~ 830 bp fragment from the SSU rDNA to identify the kleptoplasts and correlated transmission electron microscopy and nanometre-scale secondary ion mass spectrometry (TEM-NanoSIMS) isotopic imaging to study 13 C-bicarbonate, 15 N-ammonium and 34 S-sulfate uptake. In addition, respiration rate measurements were determined to assess the response of N. labradorica to light. The DNA sequences established that over 80% of the kleptoplasts belonged to Thalassiosira (with 96%-99% identity), a cosmopolitan planktonic diatom. TEM-NanoSIMS imaging revealed degraded cytoplasm and an absence of 13 C assimilation in foraminifera exposed to light. Oxygen measurements showed higher respiration rates under light than dark conditions, and no O2 production was detected. These results indicate that the photosynthetic pathways in N. labradorica are not functional. Furthermore, N. labradorica assimilated both 15 N-ammonium and 34 S-sulfate into its cytoplasm, which suggests that foraminifera might have several ammonium or sulfate assimilation pathways, involving either the kleptoplasts or bona fide foraminiferal pathway(s) not yet identified.

2D Image Quantification of Microbial Iron Chelators (Siderophores) Using Diffusive Equilibrium in Thin Films Method.

Siderophores are natural metal chelating agents that strongly control the biogeochemical metal cycles such as Fe in the environment. This article describes a new methodology to detect and quantify at the micromolar concentration the spatial distribution at millimeter scale of siderophores within the root's system. The "universal" CAS assay originally designed for bacterial siderophores detection and later designed for fungus was adapted here for diffusive equilibrium in thin film gel techniques (DET). The method was calibrated against the marketed desferrioxamine mesylate (DFOM) siderophore and applied with experiments performed with sunflower ( Helianthus annuus) and wheat ( Triticum aestivum) cultivated on free iron agar medium plates. We present here the first results with 2D images of the siderophores distribution in the vicinity of the root system of plants. With this technique we detected (i) the production of siderophores on bacteria inoculated ( Pseudomonas fluorescens) environments and (ii) hotspots of natural iron binding ligands production up to 50 µM in the wheat rhizosphere. The lower detection limit in our experiment was 2.5 µmol/L. This new technique offers a unique opportunity to investigate the siderophore production in two dimensions in a wide range of applications from laboratory experiments to natural systems very likely using an in situ and nondestructive tool.

A multiscale study of mercury transformations and dynamics at the chemocline of the Petit-Saut tropical reservoir (French Guiana).

This study investigated, on both metric and centimetric scales, mercury (Hg) transformations and dynamics within a water column chemocline of a tropical reservoir. Data collected included conventional measurement of Hg in water samples, diffusive gradients in thin-films (DGT) assessments, and thermodynamic speciation modeling in order to portray the biogeochemical processes that control elemental Hg (EM) and dissolved monomethylated Hg (MeHgD) production. The primary contribution of this study is demonstration that the DGT technique can be successfully implemented to examine labile Hg compound mobilization, and estimation of how local substratum facilitates Hg reduction and methylation reactions. DGT profiles with a resolution of 1cm revealed a fine sequence of prominent Hg reduction/oxidation reactions at the chemocline level. This is interpreted as a manifestation of both: i) kinetic effects capable of arising inside the diffusive layer of DGT devices, and ii) extremely localized production or consumption of reducible and methylable Hg. Another key result obtained at the metric scale is that EM and MeHgD production at a water column chemocline are intricately linked, as both are fueled by nutrients episodically released during the decomposition of falling epilimnetic organic particles or inhibited by dissolved organic matter and inorganic compounds continuously transported from the deeper monimolimnion. Finally, it is worth noting that the chemocline acts as an accumulation and recycling domain for falling MeHg-loaded organic particles, whereas the high primary productivity layer in the epilimnion represents the principal reactor with respect to Hg methylation and reduction.

Nutrient regeneration susceptibility under contrasting sedimentary conditions from the Rio de Janeiro coast, Brazil.

Dissolved silicate (DSi), NH4(+), NO3(-) and PO4(3-) susceptibility to be exchanged between sediment pore waters and overlying waters was evaluated in Jurujuba Sound (JS station) and Coroa Grande Sound (CGS station), southeastern Brazil. Sedimentary elemental (C, N and P) and isotopic (δ(13)C and δ(15)N) compositions evidenced stronger anthropogenic fertilization in JS station. Net NO3(-) influxes from overlying waters occurred, which was two orders of magnitude higher under the more fertilized condition. This condition resulted in 6-13-times higher net effluxes of NH4(+), DSi and PO4(3-) to overlying waters. Vertical alternation between production and consumption processes in pore waters contributed for a more limited regeneration in CGS station. This was associated with diagenetic responses to sedimentary grain size variability in deeper layers and biological disturbance in upper layers. Nearly continuous production of NH4(+), DSi and PO4(3-) in pore waters implied in intensified susceptibility to remobilization under the eutrophic condition of JS station.

Simultaneous 2D imaging of dissolved iron and reactive phosphorus in sediment porewaters by thin-film and hyperspectral methods.

This study presents a new approach combining diffusive equilibrium in thin-film (DET) and spectrophotometric methods to determine the spatial variability of dissolved iron and dissolved reactive phosphorus (DRP) with a single gel probe. Its originality is (1) to postpone up to three months the colorimetric reaction of DET by freezing and (2) to measure simultaneously dissolved iron and DRP by hyperspectral imaging at a submillimeter resolution. After a few minutes at room temperature, the thawed gel is sandwiched between two monospecific reagent DET gels, leading to magenta and blue coloration for iron and phosphate, respectively. Spatial distribution of the resulting colors is obtained using a hyperspectral camera. Reflectance spectra analysis enables deconvolution of specific colorations by the unmixing method applied to the logarithmic reflectance, leading to an accurate quantification of iron and DRP. This method was applied in the Arcachon lagoon (France) on muddy sediments colonized by eelgrass (Zostera noltei) meadows. The 2D gel probes highlighted microstructures in the spatial distribution of dissolved iron and phosphorus, which are most likely associated with the occurrence of benthic fauna burrows and seagrass roots.