Impact of peri-urban landscape on the organic and mineral contamination of pond waters and related risk assessment.

Ponds are important for their ecological value and for the ecosystem services they provide to human societies, but they are strongly affected by human activities. Peri-urban development, currently one of the most pervasive processes of land use change in Europe, exposes ponds to both urban and agricultural contaminants, causing a potential combination of adverse effects. This study, focused on 12 ponds located in a peri-urban area, has two main objectives: (1) to link the physico-chemical characteristics of the waters and the nature of their contaminants, either organic or mineral, with the human activities around ponds, and (2) to estimate the environmental risk caused by these contaminants. The ponds were sampled during two consecutive years in both spring and in autumn. Although the ponds were distributed over a limited geographical area, their contamination profiles were different and more correlated with the agricultural than the urban land use. In terms of aptitude for biology, half of the ponds were classified in degraded states due to their physico-chemical parameters, but without correlation with the endocrine disrupting activities and the levels of organic pollutants as indicators. The main quantified organic pollutants, however, were pesticides with sufficiently high levels in certain cases to induce an environmental risk exceeding the classical thresholds of risk quotient.

Soil dissipation and bioavailability to earthworms of two fungicides under laboratory and field conditions.

The representativeness of laboratory studies of the fate of pesticides in soil in field conditions is questionable. This study aimed at comparing the dissipation and bioavailability to earthworms of two fungicides, dimoxystrobin (DMX) and epoxiconazole (EPX), over 12 months under laboratory and field conditions. In both approaches, the fungicides were applied to the same loamy soil as a formulated mixture at several concentrations. We determined total DMX and EPX concentrations in the soil using exhaustive extraction, their environmental availability using mild extraction and their bioavailability through internal concentrations in exposed earthworms. The initial fungicide application appeared as much better controlled in terms of dose and homogeneity in the laboratory than in the field. One year after application, a similar dissipation rate was observed between the laboratory and field experiments (ca 80% and 60% for DMX and EPX, respectively). Similarly, the ratio of available/total concentrations in soil displayed the same trend whatever the duration and the conditions (field or lab), EPX being more available than DMX. Finally, the environmental bioavailability of the two fungicides to earthworms was heterogeneous in the field, but, in the laboratory, the bioaccumulation was evidenced to be dose-dependent only for DMX. Our findings suggest that the actual fate of the two considered fungicides in the environment is consistent with the one determined in the laboratory, although the conditions differed (e.g., presence of vegetation, endogeic earthworm species). This study allowed better understanding of the fate of the two considered active substances in the soil and underlined the need for more research dedicated to the link between environmental and toxicological bioavailability.

Impacts of one century of wastewater discharge on soil transformation through ferrolysis and related metal pollutant distributions.

Discharge of wastewater leading to notable soil surface contamination is widely reported. But few works highlight the fast dynamics of soils and their morphological transformations that may result from such anthropogenic activities. Near Paris (France), sandy Luvisols were irrigated with urban wastewater since the 1890s. Within and outside the discharge area, the soil cover presents decameter-sized cryogenic structures. We studied macro morphological soil characteristics, soil chemistry and clay mineralogy on selected bulk samples, as well as contemporary pedofeatures and related metal pollutant distribution patterns in soil thin sections from subsurface horizons. Annual repetitive waterlogging and drying cycles initiated a hydromorphic soil forming process: ferrolysis, based on iron reduction producing alkalinity under anaerobic conditions, and iron oxidation producing acidity in aerobic conditions. Its intensity was enhanced at the top of thick clay-rich B-horizons in the center of cryogenic structures. The polygonal soil structure favored the evacuating of soil water and alkalinity. Within one century, such recurrent alternating redox conditions have led to clay destruction, removal of iron, strong bleaching of the E horizon and formation of abiotic Fe-rich pedofeatures at depth. In addition, between anaerobic clay-rich B and aerated E or C horizons, the contrasting hydrodynamic conditions enhanced manganese (Mn) oxidizing fungal activity and the formation of biotic Mn-rich pedofeatures. Both types of pedofeatures trapped metal pollutants in deep soil horizons. In our work, the impacts of centenary anthropogenic activity were amplified by millenary cryogenic structures, acting together to promote fast soil dynamics, within a few decades.

High diversity of microcystins in a Microcystis bloom from an Algerian lake.

Microcystins (MCs) are cyanobacterial heptapeptides, produced by several genera and species of cyanobacteria, which have been involved in poisoning of animals throughout the world and have also been implicated in human health problems. They are regarded as the most frequently occurring and widespread of the cyanotoxins, with more than 100 MC variants reported to date including the present study. The lake des Oiseaux is a shallow permanent freshwater lake located in north-eastern Algeria. It is an important natural reserve playing a major role for the migratory birds after the crossing of the Mediterranean Sea and from the Sahara desert. In recent years, possibly related to increased eutrophication of the lake, massive blooms of cyanobacteria identified as Microcystis spp. have been observed. A bloom sample collected in September 2013 was analyzed by the serine/threonine phosphatase PP2A inhibition assay and liquid chromatography-mass spectrometry to determine respectively, the total concentration of MCs and the different variants of these toxins present. The results revealed that the Microcystis spp. bloom sample contained microcystins of which 21 putatively congeners were detected. Among these, 12 known microcystins (MC-RR, MC-LR, MC-FR, MC-WR, MC-YR, MC-LA, MC-(H4)YR, MC-HilR, [Asp(3)]MC-RAba, and [Glu(OCH3)(6)]MC-LR) and two new congeners ([Asp(3)]MC-HarAba and [Glu(OCH3)(6)]MC-FR) were characterized, considering their molecular mass and the fragment ions produced by collision-induced dissociation of the [M+H](+) ions. MC-RR was the major (43.4%) in the bloom sample.

Evaluation of the transfer and the accumulation of microcystins in tomato (Solanum lycopersicum cultivar MicroTom) tissues using a cyanobacterial extract containing microcystins and the radiolabeled microcystin-LR ((14)C-MC-LR).

Microcystins are the most common cyanotoxins and may be expected wherever blooms of cyanobacteria occur in surface waters. Their persistence both in the irrigation water and in the soil can lead to their transfer and bioaccumulation into agricultural plants. The aim of this work was to investigate microcystin accumulation in Solanum lycopersicum cultivar MicroTom. The plant was exposed to either Microcystis aeruginosa crude extracts containing up to 100 µg eq.MC-LRL(-1) in a soil-plant system for 90 days or pure radiolabeled (14)C-MC-LR in a hydroponic condition for 48 h. Toxin bioaccumulation in the soil and different plant tissues was assessed both by the PP2A inhibition assay and by liquid chromatography-mass spectrometry (LC/MS/MS). After 90 days of exposure, microcystins persisted in the soil and their free extractable concentrations accumulated were very low varying between 1.6 and 3.9 µg eq.MC-LR kg(-1) DW. Free MC-LR was detected only in roots and leaves with concentrations varying between 4.5 and 8.1 µg kg(-1) DW and between 0.29 and 0.55 µg kg(-1) DW, respectively. By using radioactivity ((14)C-MC-LR), the results have reported a growing accumulation of toxins within the organs roots>leaves>stems and allowed them to confirm the absence of MC-LR in fruits after 48 h of exposure. The bioconcentration factor (BCF) was 13.6 in roots, 4.5 in leaves, and 1.4 in stems. On the other hand, the results highlight the presence of two radioactive fractions in different plant tissues. The non-extractable fraction of radioactivity, corresponding to the covalently bound MC-LR, was higher than that of the extractable fraction only in roots and leaves reaching 56% and 71% of the total accumulated toxin, respectively. Therefore, results raise that monitoring programs must monitor the presence of MCs in the irrigation water to avoid the transfer and accumulation of these toxins in crops.

Oxidative degradation of nalidixic acid by nano-magnetite via Fe2+/O2-mediated reactions.

Organic pollution has become a critical issue worldwide due to the increasing input and persistence of organic compounds in the environment. Iron minerals are potentially able to degrade efficiently organic pollutants sorbed to their surfaces via oxidative or reductive transformation processes. Here, we explored the oxidative capacity of nano-magnetite (Fe3O4) having ∼ 12 nm particle size, to promote heterogeneous Fenton-like reactions for the removal of nalidixic acid (NAL), a recalcitrant quinolone antibacterial agent. Results show that NAL was adsorbed at the surface of magnetite and was efficiently degraded under oxic conditions. Nearly 60% of this organic contaminant was eliminated after 30 min exposure to air bubbling in solution in the presence of an excess of nano-magnetite. X-ray diffraction (XRD) and Fe K-edge X-ray absorption spectroscopy (XANES and EXAFS) showed a partial oxidation of magnetite to maghemite during the reaction, and four byproducts of NAL were identified by liquid chromatography-mass spectroscopy (UHPLC-MS/MS). We also provide evidence that hydroxyl radicals (HO(•)) were involved in the oxidative degradation of NAL, as indicated by the quenching of the degradation reaction in the presence of ethanol. This study points out the promising potentialities of mixed valence iron oxides for the treatment of soils and wastewater contaminated by organic pollutants.