Jean M. F. Martins

Tracing the Origin and Fate of NOx in the Arctic Atmosphere Using Stable Isotopes in Nitrate

Atmospheric nitrogen oxides (NOx =NO+ NO2) play a pivotal role in the cycling of reactive nitrogen (ultimately deposited as nitrate) and the oxidative capacity of the atmosphere. Combined measurements of nitrogen and oxygen stable isotope ratios of nitrate collected in the Arctic atmosphere were used to infer the origin and fate of NOx and nitrate on a seasonal basis. In spring, photochemically driven emissions of reactive nitrogen from the snowpack into the atmosphere make local oxidation of NOx by bromine oxide the major contributor to the nitrate budget. The comprehensive isotopic composition of nitrate provides strong constraints on the relative importance of the key atmospheric oxidants in the present atmosphere, with the potential for extension into the past using ice cores.

Comprehensive isotopic composition of atmospheric nitrate in the Atlantic Ocean boundary layer from 65°S to 79°N

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the δ 15N of nitrate mostly deriving from anthropogenically emitted NO x is found to be significantly different (from 0 to 6‰) from nitrate sampled in locations influenced by natural NO x sources (−4 ± 2)‰. The effects on δ 15N(NO3 −) of different NO x sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (Δ17O = δ 17O − 0.52 × δ 18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NO x sinks. Different Δ17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low δ 15N values (down to −40‰) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NO x from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

Influence of soil properties on the toxicity of TiO2 nanoparticles on carbon mineralization and bacterial abundance

Information regarding the impact of low concentration of engineered nanoparticles on soil microbial communities is currently limited and the importance of soil characteristics is often neglected in ecological risk assessment. To evaluate the impact of TiO2 nanoparticles (NPs) on soil microbial communities (measured on bacterial abundance and carbon mineralization activity), 6 agricultural soils exhibiting contrasted textures and organic matter contents were exposed for 90 days to a low environmentally relevant concentration or to an accidental spiking of TiO2-NPs (1 and 500mgkg(-1) dry soil, respectively) in microcosms. In most soils, TiO2-NPs did not impact the activity and abundance of microbial communities, except in the silty-clay soil (high OM) where C-mineralization was significantly lowered, even with the low NPs concentration. Our results suggest that TiO2-NPs toxicity does not depend on soil texture but likely on pH and OM content. We characterized TiO2-NPs aggregation and zeta potential in soil solutions, in order to explain the difference of TiO2-NPs effects on soil C-mineralization. Zeta potential and aggregation of TiO2-NPs in the silty-clay (high OM) soil solution lead to a lower stability of TiO2-NP-aggregates than in the other soils. Further experiments would be necessary to evaluate the relationship between TiO2-NPs stability and toxicity in the soil.

Effect of long term organic amendments and vegetation of vineyard soils on the microscale distribution and biogeochemistry of copper

In this study we evaluated the effect of the long term organic management of a vineyard-soil on the biogeochemistry of copper at the micro-aggregate scale. The model vineyard-soil (Mâcon-France) experienced a long-term field-experiment that consisted in amendments and vegetations with various materials and plants. We studied specifically the effect of Straw (S) and Conifer Compost (CC) organic amendments and Clover (Cl) and Fescue (F) vegetation on the fate of copper (fungicide) in the surface layer of this loamy soil, through a comparison with the Non Amended soil (NA). After collection the five soils were immediately physically fractionated in order to obtain 5 granulometric size-fractions. All soils and size-fractions were quantitatively characterized in terms of granulometry, chemical content and copper distribution, speciation and bioavailability to bacteria and plants. The results showed strong increases of soil-constituents aggregation for all treatments (Cl>CC>S>F>NA), in relation with the increased cementation of soil-constituents by organic matter (OM). The distribution patterns of all major elements and organic carbon were found highly variable within the soil sub-fractions and also between the 5 treatments. Due to their specific inorganic and organic composition, soil sub-fractions can thus be considered as a specific microbial habitat. Added OM accumulated preferentially in the 20-2 μm and in the >250 μm of the 5 soils. The distribution patterns of copper as well as its speciation and bioavailability to bacteria in the soil sub-fractions were shown to be strongly different among the five soils, in relation with OM distribution. Our results also suggest that Cu-bioavailability to plants is controlled by soil-rhizosphere structure. Altogether our results permitted to show that long-term organic management of a vineyard soil induced stable modifications of soil physical and chemical properties at both macro and micro-scales. These modifications affected in turn the micro-scale biogeochemistry of copper, and especially its bioavailability to bacteria and plants.

Antibiotic pollution in the Katari subcatchment of the Titicaca Lake: Major transformation products and occurrence of resistance genes

An increasing number of studies pointed out the ubiquitous presence of medical residues in surface and ground water as well as in soil compartments. Not only antibiotics can be found in the environment but also their transformation products about which little information is generally available. The development of bacterial resistance to antibiotics is particularly worrying as it can lead to sanitary and health problems. Studies about the dissemination of antibiotics and associated resistances in the Bolivian Altiplano are scarce. We provide baseline information on the occurrence of Sulfamethoxazole (SMX) and Trimethoprim (TMP) antibiotics as well as on the most common human SMX transformation products (TP) and on the occurrence of sulfonamide resistance genes. The studied water and soil compartments presented high levels of antibiotic pollution. This situation was shown to be mainly linked with uncontrolled discharges of treated and untreated wastewaters, resulting on the presence of antibiotics in the Titicaca Lake. SMX TPs were detected in surface waters and on soil sampled next to the wastewater treatment plant (WWTP). SMX resistance genes sulI and sulII were widely detected in the basin hydrological network, even in areas unpolluted with antibiotics. Mechanisms of co-selection of antibiotic- and metal- resistance may be involved in the prevalence of ARGs in pristine areas with no anthropogenic activity and free of antibiotic pollution.

Comparison of three labeled silica nanoparticles used as tracers in transport experiments in porous media. Part II: transport experiments and modeling.

Three types of labeled silica nanoparticles were used in transport experiments in saturated sand. The goal of this study was to evaluate both the efficiency of labeling techniques (fluorescence (FITC), metal (Ag(0) core) and radioactivity ((110m)Ag(0) core)) in realistic transport conditions and the reactive transport of silica nanocolloids of variable size and concentration in porous media. Experimental results obtained under contrasted experimental conditions revealed that deposition in sand is controlled by nanoparticles size and ionic strength of the solution. A mathematical model is proposed to quantitatively describe colloid transport. Fluorescent labeling is widely used to study fate of colloids in soils but was the less sensitive one. Ag(0) labeling with ICP-MS detection was found to be very sensitive to measure deposition profiles. Radiolabeled ((110m)Ag(0)) nanoparticles permitted in situ detection. Results obtained with radiolabeled nanoparticles are wholly original and might be used for improving the modeling of deposition and release dynamics.

Comparison of three labeled silica nanoparticles used as tracers in transport experiments in porous media. Part I: syntheses and characterizations.

The synthesis and the characterization of three kinds of labeled silica nanoparticles were performed. Three different labeling strategies were investigated: fluorescent organic molecule (FITC) embedded in silica matrix, heavy metal core (Ag(0)) and radioactive core ((110m)Ag) surrounded by a silica shell. The main properties and the suitability of each kind of labeled nanoparticle in terms of size, surface properties, stability, detection limits, and cost were determined and compared regarding its use for transport studies. Fluorescent labeling was found the most convenient and the cheapest, but the best detection limits were reached with chemical (Ag(0)) and radio-labeled ((110m)Ag) nanoparticles, which also allowed nondestructive quantifications. This work showed that the choice of labeled nanoparticles as surrogates of natural colloids or manufactured nanoparticles strongly depends on the experimental conditions, especially the concentration and amount required, the composition of the effluent, and the timescale of the experiment.

The unexpected role of bioaerosols in the Oxidative Potential of PM

AbstractBioaerosols represent up to 15–25% of PM by mass, but there is currently no assessment of their impact on Oxidative Potential (OP), or capacity of particulate matter (PM) to produce damaging oxidative reactions in the human lungs. Here, the OP of selected bioaerosols (bacteria cells vs fungal spores) was assessed through the cell-free DTT assay. Results show that bioaerosols induce Reactive Oxygen Species (ROS) production, varying along the microorganism type, species, and concentration. Fungal spores show up to 10 times more ROS generation than bacterial cells. At the highest concentrations, fungal spores present as much oxidative reactivity as the most redox-active airborne chemicals (Copper, Naphtoquinone). Moreover, bioaerosols substantially influence OP of ambient PM and that of its chemical constituents: in presence of A. fumigatus spores, the OP of Cu/NQ is increased by a factor of 2 to 5, whereas, 104 and 105  S. epidermidis bacterial cells.mL−1 halves the OP of Cu/NQ. Finally, viable and gamma-rays-killed model bioaerosols present similar oxidative reactivity, suggesting a metabolism-independent cellular mechanism. These results reveal the importance of bioaerosols for PM reactivity. PM toxicity can be modified due to bioaerosols contribution or by their ability to modulate the OP of toxic chemicals present in PM.

Titanium dioxide nanoparticles strongly impact soil microbial function by affecting archaeal nitrifiers.

Soils are facing new environmental stressors, such as titanium dioxide nanoparticles (TiO2-NPs). While these emerging pollutants are increasingly released into most ecosystems, including agricultural fields, their potential impacts on soil and its function remain to be investigated. Here we report the response of the microbial community of an agricultural soil exposed over 90 days to TiO2-NPs (1 and 500 mg kg−1 dry soil). To assess their impact on soil function, we focused on the nitrogen cycle and measured nitrification and denitrification enzymatic activities and by quantifying specific representative genes (amoA for ammonia-oxidizers, nirK and nirS for denitrifiers). Additionally, diversity shifts were examined in bacteria, archaea, and the ammonia-oxidizing clades of each domain. With strong negative impacts on nitrification enzyme activities and the abundances of ammonia-oxidizing microorganism, TiO2-NPs triggered cascading negative effects on denitrification enzyme activity and a deep modification of the bacterial community structure after just 90 days of exposure to even the lowest, realistic concentration of NPs. These results appeal further research to assess how these emerging pollutants modify the soil health and broader ecosystem function.

Reactivity of the plant growth regulator paclobutrazol (cultar) with two tropical soils of the northeast semiarid region of Brazil.

The reactivity of paclobutrazol (PBZ, a plant growth retardant) with a Yellow Ultisol and a Vertisol from the semiarid northeast region of Brazil was evaluated through batch sorption experiments and modeling. Although not instantaneous, the sorption kinetic of PBZ (pure and formulated) was fast (a few hours) in both soils. The sorption kinetics were well described by a second-order (dS(t)/dt=k(2)(S(e2)-S(t))(2)) but not by a first-order model. The sorption isotherms were found to be linear and the calculated K(D) values were 8.8 +/- 0.11 and 7.4 +/- 0.2 L kg(-1) for pure PBZ in the Ultisol and the Vertisol, respectively. The corresponding K(OC) values were 1275 +/- 34 (logK(OC) = 3.11) and 1156 +/- 49 (logK(OC) = 3.06) L kg(-1), respectively. Considering the very different texture of the two soils and the similar K(OC) values determined, these results showed that in both soils, the sorption of PBZ is dominantly controlled by organic matter, although some interactions of PBZ with iron oxides (goethite) were observed in the Ultisol. Based on these sorption parameters a low leachability potential of PBZ in soils is anticipated, as they correspond to a groundwater ubiquity score (GUS) ranging from 2.0 to 2.7, i.e., moderately to not mobile, in contradiction with the actual groundwater situation in Brazil. This work stresses the need to evaluate and predict the risk associated with aquifer contamination by this widely used plant growth regulator.