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.

Aragonite saturation state in a tropical coastal embayment dominated by phytoplankton blooms (Guanabara Bay - Brazil).

The dynamics of the aragonite saturation state (Ωarag) were investigated in the eutrophic coastal waters of Guanabara Bay (RJ-Brazil). Large phytoplankton blooms stimulated by a high nutrient enrichment promoted the production of organic matter with strong uptake of dissolved inorganic carbon (DIC) in surface waters, lowering the concentrations of dissolved carbon dioxide (CO2aq), and increasing the pH, Ωarag and carbonate ion (CO32-), especially during summer. The increase of Ωarag related to biological activity was also evident comparing the negative relationship between the Ωarag and the apparent utilization of oxygen (AOU), with a very close behavior between the slopes of the linear regression and the Redfield ratio. The lowest values of Ωarag were found at low-buffered waters in regions that receive direct discharges from domestic effluents and polluted rivers, with episodic evidences of corrosive waters (Ωarag<1). This study showed that the eutrophication controlled the variations of Ωarag in Guanabara Bay.

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.

X-ray microanalysis of porous materials using Monte Carlo simulations.

Quantitative X-ray microanalysis models, such as ZAF or φ(ρz) methods, are normally based on solid, flat-polished specimens. This limits their use in various domains where porous materials are studied, such as powder metallurgy, catalysts, foams, etc. Previous experimental studies have shown that an increase in porosity leads to a deficit in X-ray emission for various materials, such as graphite, Cr(2) O(3) , CuO, ZnS (Ichinokawa et al., '69), Al(2) O(3) , and Ag (Lakis et al., '92). However, the mechanisms responsible for this decrease are unclear. The porosity by itself does not explain the loss in intensity, other mechanisms have therefore been proposed, such as extra energy loss by the diffusion of electrons by surface plasmons generated at the pores-solid interfaces, surface roughness, extra charging at the pores-solid interface, or carbon diffusion in the pores. However, the exact mechanism is still unclear. In order to better understand the effects of porosity on quantitative microanalysis, a new approach using Monte Carlo simulations was developed by Gauvin (2005) using a constant pore size. In this new study, the X-ray emissions model was modified to include a random log normal distribution of pores size in the simulated materials. This article presents, after a literature review of the previous works performed about X-ray microanalysis of porous materials, some of the results obtained with Gauvin's modified model. They are then compared with experimental results.

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.