Synergies of chemodenitrification and denitrification in a saline inland lake.

The interconnection between biotic and abiotic pathways involving the nitrogen and iron biogeochemical cycles has recently gained interest. While lacustrine ecosystems are considered prone to the biotic nitrate reduction (denitrification), their potential for promoting the abiotic nitrite reduction (chemodenitrification) remains unclear. In the present study, batch incubations were performed to assess the potential for chemodenitrification and denitrification in the saline inland lake Gallocanta. Sulfidic conditions are found in top sediments of the system while below (5-9 cm), it presents low organic carbon and high sulfate and ferrous iron availability. Anoxic incubations of sediment (5-9 cm) and water from the lake with nitrite revealed potential for chemodenitrification, especially when external ferrous iron was added. The obtained isotopic fractionation values for nitrite (ɛ15NNO2) were -6.8 and -12.3 ‰ and therefore, fell in the range of those previously reported for the nitrite reduction. The more pronounced ɛ15NNO2 (-12.3 ‰) measured in the experiment containing additional ferrous iron was attributed to a higher contribution of the chemodenitrification over biotic denitrification. Incubations containing nitrate also confirmed the potential for denitrification under autotrophic conditions (low organic carbon, high ferrous iron). Higher reaction rate constants were found in the experiment containing 100 µM compared to 400 µM nitrate. The obtained ɛ15NNO3 values (-8.5 and -15.1 ‰) during nitrate consumption fell in the range of those expected for the denitrification. A more pronounced ɛ15NNO3 (-15.1 ‰) was determined in the experiment presenting a lower reaction rate constant (400 µM nitrate). Therefore, in Gallocanta lake, nitrite generated during nitrate reduction can be further reduced by both the abiotic and biotic pathways. These findings establish the significance of chemodenitrification in lacustrine systems and support further exploration in aquatic environments with different levels of C, N, S, and Fe. This might be especially useful in predicting nitrous oxide emissions in natural ecosystems.

Upside down sulphate dynamics in a saline inland lake.

The sulphur cycle has a key role on the fate of nutrients through its several interconnected reactions. Although sulphur cycling in aquatic ecosystems has been thoroughly studied since the early 70's, its characterisation in saline endorheic lakes still deserves further exploration. Gallocanta Lake (NE Spain) is an ephemeral saline inland lake whose main sulphate source is found on the lake bed minerals and leads to dissolved sulphate concentrations higher than those of seawater. An integrative study including geochemical and isotopic characterization of surface water, porewater and sediment has been performed to address how sulphur cycling is constrained by the geological background. In freshwater and marine environments, sulphate concentration decreases with depth are commonly associated with bacterial sulphate reduction (BSR). However, in Gallocanta Lake sulphate concentrations in porewater increase from 60 mM at the water-sediment interface to 230 mM at 25 cm depth. This extreme increase could be caused by dissolution of the sulphate rich mineral epsomite (MgSO4·7H2O). Sulphur isotopic data was used to validate this hypothesis and demonstrate the occurrence of BSR near the water-sediment interface. This dynamic prevents methane production and release from the anoxic sediment, which is advantageous in the current context of global warming. These results underline that geological context should be considered in future biogeochemical studies of inland lakes with higher potential availability of electron acceptors in the lake bed compared to the water column.

Corrigendum: Invasive Aquatic Plants as Ecosystem Engineers in an Oligo-Mesotrophic Shallow Lake.

[This corrects the article DOI: 10.3389/fpls.2018.01781.].

Drivers of variability in mercury and methylmercury bioaccumulation and biomagnification in temperate freshwater lakes.

The four largest freshwater lakes in southwestern France are of both ecological and economic importance. However, some of them are subjected to mercury (Hg) contamination, resulting in the ban of human consumption of piscivorous fish. Moreover, beyond predatory fish, little information exist regarding Hg levels in other species of these ecosystems. In this context, we used a food web analytical approach to investigate Hg bioaccumulation and biomagnification in relation to the trophic structure of these four lakes. More specifically, various organisms (macrophytes, epiphyton, invertebrates and fish) were collected at the four lakes and analysed for carbon and nitrogen stable isotopes as well as for total Hg (THg) and methylmercury (MeHg). A spatial variability of bioaccumulation in organisms was observed, particularly in carnivorous fish, with higher Hg levels being found in the two more northern lakes (median±SE: 3491 ± 474 and 1113 ± 209 ng THg.g-1 dw in lakes HC and L, respectively) than in the southern pair (600 ± 117 and 911 ± 117 ng THg.g-1 dw in lakes CS and PB, respectively). Methylmercury biomagnification was observed through the food webs of all four lakes, with different trophic magnification slopes (HC = 0.16; L = 0.33; CS = 0.27; PB = 0.27), even though the length of the food chains was similar between the lakes. Our results suggest that rather than the food web structure, anthropogenic inputs (sulfate in northern lakes and phosphorus inputs in southern ones) may have a strong impact, more or less directly, on Hg methylation in freshwater environments, and lead to concentrations exceeding environmental recommendations despite low Hg backgrounds in sediment and water.

Importance of the vegetation-groundwater-stream continuum to understand transformation of biogenic carbon in aquatic systems - A case study based on a pine-maize comparison in a lowland sandy watershed (Landes de Gascogne, SW France).

During land-aquatic transfer, carbon (C) and inorganic nutrients (IN) are transformed in soils, groundwater, and at the groundwater-surface water interface as well as in stream channels and stream sediments. However, processes and factors controlling these transfers and transformations are not well constrained, particularly with respect to land use effect. We compared C and IN concentrations in shallow groundwater and first-order streams of a sandy lowland catchment dominated by two types of land use: pine forest and maize cropland. Contrary to forest groundwater, crop groundwater exhibited oxic conditions all-year round as a result of higher evapotranspiration and better lateral drainage that decreased the water table below the organic-rich soil horizon, prevented the leaching of soil-generated dissolved organic carbon (DOC) in groundwater, and thus limited consumption of dissolved oxygen (O2). In crop groundwater, oxic conditions inhibited denitrification and methanogenesis resulting in high nitrate (NO3-; on average 1140 ±â€¯485 µmol L-1) and low methane (CH4; 40 ±â€¯25 nmol L-1) concentrations. Conversely, anoxic conditions in forest groundwater led to lower NO3- (25 ±â€¯40 µmol L-1) and higher CH4 (1770 ±â€¯1830 nmol L-1) concentrations. The partial pressure of carbon dioxide (pCO2; 30,650 ±â€¯11,590 ppmv) in crop groundwater was significantly lower than in forest groundwater (50,630 ±â€¯26,070 ppmv), and was apparently caused by the deeper water table delaying downward diffusion of soil CO2 to the water table. In contrast, pCO2 was not significantly different in crop (4480 ±â€¯2680 ppmv) and forest (4900 ±â€¯4500 ppmv) streams, suggesting faster degassing in forest streams resulting from greater water turbulence. Although NO3-concentrations indicated that denitrification occurred in riparian-forest groundwater, crop streams nevertheless exhibited important signs of spring and summer eutrophication such as the development of macrophytes. Stream eutrophication favored development of anaerobic conditions in crop stream sediments, as evidenced by increased ammonia (NH4+) and CH4 in stream waters and concomitant decreased in NO3- concentrations as a result of sediment denitrification. In crop streams, dredging and erosion of streambed sediments during winter sustained high concentration of particulate organic C, NH4+ and CH4. In forest streams, dissolved iron (Fe2+), NH4+ and CH4 were negatively correlated with O2 reflecting the gradual oxygenation of stream water and associated oxidations of Fe2+, NH4+ and CH4. The results overall showed that forest groundwater behaved as source of CO2 and CH4 to streams, the intensity depending on the hydrological connectivity among soils, groundwater, and streams. CH4 production was prevented in cropland in soils and groundwater, however crop groundwater acted as a source of CO2 to streams (but less so than forest groundwater). Conversely, in streams, pCO2 was not significantly affected by land use while CH4 production was enhanced by cropland. At the catchment scale, this study found substantial biogeochemical heterogeneity in C and IN concentrations between forest and crop waters, demonstrating the importance of including the full vegetation-groundwater-stream continuum when estimating land-water fluxes of C (and nitrogen) and attempting to understand their spatial and temporal dynamics.

Spectrophotometric determination of manganese in acidified matrices from (pore)waters and from sequential leaching of sediments.

Manganese (Mn) is a major redox reactive element in marine sediments and it plays an important role in the biogeochemical cycles of carbon, nitrogen, phosphorus, or trace metals. Mn cycle in marine sediments is characterized by an alternation of oxidation and reduction processes depending on physicochemical and biological conditions: assessing the quantification and the speciation of Mn is thus an essential issue to understand redox reaction-transport processes in sedimentary deposits. Solid Mn phases can be determined through chemical extractions techniques that permits selective leaching of operationally defined Mn fractions. Mn oxides and oxyhydroxides are extracted with an ascorbate leaching solution, while the whole Mn (oxyhydr-)oxides and Mn associated to carbonates is extracted with HCl. An existing spectrophotometric method allows to quantify Mn dissolved in (sea) water. We present here a modified version, which permits to measure Mn in acidified matrices, including ascorbate and HCl solutions. A metallic substitution occurs between a Cd-TCPP complex and Mn at pH 7.5-8.0, with imidazole as catalyst. We propose here to use a NaHCO3 solution to dilute the samples in order to be in the necessary pH range to perform the metal substitution. Using this method, Mn(II,III) concentrations were determined in standard solutions with a precision of 3% within a concentration range of 0.5-80 µM. The procedure was successfully applied to determine Mn in acidified pore waters and in ascorbate and HCl sequential extractions from muddy sediments of the Bay of Biscay. Spectrophotometric results agreed closely with results from atomic absorption spectrometry, validating the proposed method.

Invasive Aquatic Plants as Ecosystem Engineers in an Oligo-Mesotrophic Shallow Lake.

Exotic hydrophytes are often considered as aquatic weeds, especially when forming dense mats on an originally poorly colonized environment. While management efforts and research are focused on the control and on the impacts of aquatic weeds on biodiversity, their influence on shallow lakes' biogeochemical cycles is still unwell explored. The aim of the present study is to understand whether invasive aquatic plants may affect the biogeochemistry of shallow lakes and act as ecosystem engineers. We performed a multi-year investigation (2013-2015) of dissolved biogeochemical parameters in an oligo-mesotrophic shallow lake of south-west of France (Lacanau Lake), where wind-sheltered bays are colonized by dense mats of exotic Egeria densa Planch. and Lagarosiphon major (Ridl.) Moss. We collected seasonal samples at densely vegetated and plant-free areas, in order to extrapolate and quantify the role of the presence of invasive plants on the biogeochemistry, at the macrophyte stand scale and at the lake scale. Results revealed that elevated plant biomass triggers oxygen (O2), dissolved inorganic carbon (DIC) and nitrogen (DIN) stratification, with hypoxia events frequently occurring at the bottom of the water column. Within plants bed, elevated respiration rates generated important amounts of carbon dioxide (CO2), methane (CH4) and ammonium (NH4 +). The balance between benthic nutrients regeneration and fixation into biomass results strictly connected to the seasonal lifecycle of the plants. Indeed, during summer, DIC and DIN regenerated from the sediment are quickly fixed into plant biomass and sustain elevated growth rates. On the opposite, in spring and autumn, bacterial and plant respiration overcome nutrients fixation, resulting in an excess of nutrients in the water and in the increase of carbon emission toward the atmosphere. Our study suggests that aquatic weeds may perform as ecosystem engineers, by negatively affecting local oxygenation and by stimulating nutrients regeneration.

A comprehensive study of the toxicity of natural multi-contaminated sediments: New insights brought by the use of a combined approach using the medaka embryo-larval assay and physico-chemical analyses.

Sediment compartment is a long term sink for pollutants and a secondary source of contamination for aquatic species. The abiotic factors controlling the bioavailability and thus the toxicity of complex mixtures of pollutants accumulated in sediments are poorly documented. To highlight the different factors influencing sediment toxicity, we identified and analyzed the physico-chemical properties, micro-pollutant contents, and toxicity level of six contrasted sediments in the Lot-Garonne continuum. Sediment toxicity was evaluated using the recently described Japanese medaka (Oryzias latipes) embryo-larval assay with direct exposure to whole sediment (MELAc). Multiple toxicity endpoints including embryotoxicity, developmental defects and DNA damage were analyzed in exposed embryos. Chemical analyses revealed significant variations in the nature and contamination profile of sediments, mainly impacted by metallic trace elements and, unexpectedly, polycyclic aromatic hydrocarbons. Exposure to sediments induced different toxic impacts on medaka early life stages when compared with the reference site. Principal component analysis showed that the toxic responses following exposure to sediments from the Lot River and its tributary were associated with micro-pollutant contamination: biometric measurements, hatching success, genotoxicity, craniofacial deformities and yolk sac malabsorption were specifically correlated to metallic and organic contaminants. Conversely, the main biological responses following exposure to the Garonne River sediments were more likely related to their physico-chemical properties than to their contamination level. Time to hatch, cardiovascular injuries and spinal deformities were correlated to organic matter content, fine particles and dissolved oxygen levels. These results emphasize the necessity of combining physico-chemical analysis of sediment with toxicity assessment to accurately evaluate the environmental risks associated with sediment contamination.

Assessing the toxicity of sediments using the medaka embryo-larval assay and 2 other bioassays.

Sediments are sinks for aquatic pollutants, and analyzing toxicity in such complex matrices is still challenging. To evaluate the toxicity of bioavailable pollutants accumulated in sediments from the Bizerte lagoon (Tunisia), a novel assay, the medaka embryo-larval assay by sediment contact, was applied. Japanese medaka (Oryzias latipes) embryos were incubated in direct contact with sediment samples up to hatching. Lethal and sublethal adverse effects were recorded in embryos and larvae up to 20 d postfertilization. Results from medaka embryo-larval assay were compared with cytotoxicity (Microtox®), genotoxicity (SOS chromotest), and pollutant content of sediments. The results highlight differences in the contamination profile and toxicity pattern between the different studied sediments. A significant correlation was shown between medaka embryo-larval assay by sediment contact and SOS chromotest responses and concentrations of most organic pollutants studied. No correlation was shown between pollutant levels and Microtox. According to the number of sediment samples detected as toxic, medaka embryo-larval assay by sediment contact was more sensitive than Microtox, which in turn was more sensitive than the SOS chromotest; and medaka embryo-larval assay by sediment contact allowed sediment toxicity assessment of moderately polluted sediments without pollutant extraction and using an ecologically realistic exposure scenario. Although medaka embryo-larval assay by sediment contact should be tested on a larger sample set, the results show that it is sensitive and convenient enough to monitor the toxicity of natural sediments. Environ Toxicol Chem 2016;35:2270-2280. © 2016 SETAC.

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.

A new spiked sediment assay using embryos of the Japanese medaka specifically designed for a reliable toxicity assessment of hydrophobic chemicals.

Despite their low water solubility, hydrophobic pollutants are widespread in the aquatic environment and could represent a threat for living organisms. EU regulations on chemicals require accurate and reliable data on chemical toxicity. Current normalised fish toxicity assays, in particular those advocated by OECD guidelines, do not allow reliable toxicity assessment of hydrophobic compounds due to their low water solubility. In order to accurately evaluate the toxicity of this kind of compounds, a new spiked sediment assay using embryos of the Japanese medaka was developed. It consists of directly exposing fertilised eggs, during their entire embryonic development, onto the reference sediment spiked with the test compound. A large set of lethal or sublethal effects in embryos and newly hatched larvae, including non-invasive endpoints is analysed in order to maximise the sensitivity of the test. The approach was validated using four model pollutants with different modes of action: DMBA, PCB126, PCB153 and 4-nonylphenol (NP). All compounds, except PCB153, induced a dose-dependent increase in toxic effects. In fact, lethal effects only occurred at the highest tested concentration. In contrast, sub-lethal effects including skeletal deformations, cardiac activity modulation, body length reduction and hatching delay were observed at low to moderate concentrations of DMBA and PCB126. NP induced subtle effects in embryos, altering cardiac activity and hatching success but only at high concentrations. Although a few more improvements would make it a fully standardised assay, this spiked sediment assay using medaka embryos proves to be sensitive enough to measure hydrophobic chemical toxicity using an environmentally realistic mode of exposure.

Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification.

Impact of solid waste disposal on nutrient dynamics in a sandy catchment.

Groundwaters impacted by mature landfill leachate are generally enriched in ammonium. In order to assess the dynamics of ammonium exchanges between leachates and the water system inside a sandy permeable catchment we measured ammonium, nitrate and chloride concentrations in the stream and in sediment pore waters of the streambed of a landfill impacted aquifer. Geophysical investigation methods complemented the biogeochemical survey. The studied zone is a 23 km(2) catchment located in a coastal lagoon area sensitive to eutrophication risk. Ammonium concentrations in the river were up to 800 micromol l(-1) during low water period in summer. Three surveys of the river chemistry showed a regular increase in ammonium, nitrate and chloride concentrations along a 1 km section of the watercourse, downstream the landfill, implying that the leachate plume exfiltrates along this section. Sediment cores collected within this section showed all an increase in ammonium concentrations with depth in pore waters as a consequence of the landfill leachate dispersion, as attested by a simultaneous increase in chloride concentrations. Nitrate enrichment in the river water was due to nitrification of ammonium at the interface between groundwater and streamwater. The apparent nitrification rate obtained was within values reported for turbid estuaries, although the river contained very little suspended particulate matter. Actually, pore water chemistry suggests that nitrification occurred for the most part in subsurface permeable sediments, rather than in stream water. The overall topographic, hydrological, geochemical, and geoelectrical data set permit to estimate the extension of the chloride and ammonium plume. The estimation of the apparent ammonium plume velocity is 23 m year(-1) whereas the chloride plume velocity should be 50 m year(-1). The river is the outlet of the impacted groundwaters. Considering that the input of ammonium from the landfill is balanced by the present day output via the river, the residence time of ammonium in the aquifer is between 7 and 18 years.

Effects of bioturbation on cadmium transfer and distribution into freshwater sediments.

To investigate bioturbation effects on cadmium (Cd) fluxes from overlying water to sediments, indoor microcosms were developed. The bioturbating organisms were freshwater tubificid worms. Three experimental conditions were studied during 56 d. The three conditions were contaminated water column ([Cd]: 20 microg/L) with or without worms and uncontaminated water column with worms. Cadmium vertical profiles were determined in the pore water and in the sediments, based on six layers (0-0.5, 0.51, 1-2, 2-3, 3-5, 5-12 cm). Dissolved oxygen, manganese, sulfate, and particulate manganese were measured. Bioturbation was analyzed using conservative fluorescent particulate tracers. Bioturbation increased Cd flux into the sediments by close to a factor of two. Scavenging of Cd was more efficient in the bioturbated sediments because particles and adsorption sites for Cd were renewed at the sediment-water interface. Tubificids also increased the thickness of the Cd-enriched layer. Metals adsorbed on particles at the sediment surface were distributed by bioadvection, which predominated the mixing processes. Bioturbation also modified the vertical profiles of dissolved and particulate manganese and dissolved sulfate but not the profiles of dissolved oxygen. These results indicate that the advective transport of particles by bioturbation and their subsequent modification by redox reactions accelerates the trapping of metals in sediments.

Cadmium bioaccumulation in Tubificidae from the overlying water source and effects on bioturbation.

Cadmium bioaccumulation in tubificid oligochaetes in relation to metal vertical distribution in sediment and bioturbation intensity was studied during a 56-day experiment with a constant contamination source in the overlying water (20 microg L(-1)). The indoor microcosms simulate a two-compartment biotope with three experimental treatments based on metal exposure and faunal composition: contaminated water column with or without worms and uncontaminated water column with worms. Cadmium bioaccumulation in worms was studied after 7, 14, 21, 28, and 56 days. Bioturbation was analyzed as a functional parameter representative of organisms' activity and using conservative particulate tracers: luminophores (phi = 63-100 microm and 100-315 microm) and microspheres (phi = 1 microm). The results show no significant effects of cadmium exposure on bioturbation, despite high bioaccumulation levels in worms (50 microg g(-1) dry wt.), suggesting the existence of detoxification/sequestration processes.